(Topics in Organometallic Chemistry 40) Gerard Van Koten (Auth.), Gerard Van Koten, David Milstein (Eds.) - Organometallic Pincer Chemistry-Springer-Verlag Berlin Heidelberg (2013)
(Topics in Organometallic Chemistry 40) Gerard Van Koten (Auth.), Gerard Van Koten, David Milstein (Eds.) - Organometallic Pincer Chemistry-Springer-Verlag Berlin Heidelberg (2013)
(Topics in Organometallic Chemistry 40) Gerard Van Koten (Auth.), Gerard Van Koten, David Milstein (Eds.) - Organometallic Pincer Chemistry-Springer-Verlag Berlin Heidelberg (2013)
Editorial Board:
M. Beller J. M. Brown P. H. Dixneuf
l l
With Contributions by
Editorial Board
Prof. Matthias Beller Prof. Louis S. Hegedus
Leibniz-Institut für Katalyse e.V. Department of Chemistry
an der Universität Rostock Colorado State University
Albert-Einstein-Str. 29a Fort Collins, Colorado 80523-1872, USA
18059 Rostock, Germany [email protected]
[email protected]
Prof. Peter Hofmann
Prof. John M. Brown Organisch-Chemisches Institut
Chemistry Research Laboratory Universität Heidelberg
Oxford University Im Neuenheimer Feld 270
Mansfield Rd., 69120 Heidelberg, Germany
Oxford OX1 3TA, UK [email protected]
[email protected]
Prof. Takao Ikariya
Prof. Pierre H. Dixneuf Department of Applied Chemistry
Graduate School of Science and Engineering
Campus de Beaulieu Tokyo Institute of Technology
Université de Rennes 1 2-12-1 Ookayama, Meguro-ku,
Av. du Gl Leclerc Tokyo 152-8552, Japan
35042 Rennes Cedex, France [email protected]
[email protected]
Prof. Luis A. Oro
Prof. Alois Fürstner Instituto Universitario de Catálisis Homogénea
Max-Planck-Institut für Kohlenforschung Department of Inorganic Chemistry
Kaiser-Wilhelm-Platz 1 I.C.M.A. - Faculty of Science
45470 Mülheim an der Ruhr, Germany University of Zaragoza-CSIC
[email protected] Zaragoza-50009, Spain
[email protected]
Prof. Lukas J. Gooßen Prof. Qi-Lin Zhou
FB Chemie - Organische Chemie State Key Laboratory of Elemento-organic
TU Kaiserslautern Chemistry
Erwin-Schrödinger-Str. Geb. 54 Nankai University
67663 Kaiserslautern, German Weijin Rd. 94, Tianjin 300071 PR China
[email protected] [email protected]
.
Topics in Organometallic Chemistry
Also Available Electronically
E'
C M Ln
Fig. 1 Representation of the ECE0 pincer–metal complexes with a central s–M–C bond of a MLn
fragment to the monoanionic carbon centre (E and E0 are neutral donor atom groupings) featuring in
the chemistry covered in this volume. Note that in most compounds, the pincer ligand acts as a 6e
ligand with both E and E0 coordinating to M, see also Fig. 2 in ref. [13].
ix
x Preface
References
xi
xii Contents
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
Top Organomet Chem (2013) 40: 1–20
DOI: 10.1007/978-3-642-31081-2_1
# Springer-Verlag Berlin Heidelberg 2013
Abstract During the past 40 years, the monoanionic, tridentate ligand platform
that has been named “Pincer” has established itself as a privileged ligand in a
variety of research and application areas. Exciting discoveries with NCN and PCP-
pincer metal complexes in the late 1970s created a firm basis for the tremendous
development of the field. Some of the basic findings are summarized with emphasis
on the organometallic aspects of the ECE-pincer metal system.
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Coordination Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3 Preparation of Pincer-Metal Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4 Stability and Decomposition Pathways
of Pincer-Metal Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5 Reactions with Electrophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6 Reactions with Small Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
7 Pincer Complexes with Unusual Formal Oxidation States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
- Length of arm; X is
CH2, NH or O - Donor groupings can be
- (Chiral) substituents alike or different
X E
- Substituents R
- Nano-sized object - Choice of metal
- Type of ring - Site for counter ions
C MLn or ancillary ligands
Rx
X E" - Choice of 2e donor atom
-Type of Cipso - Substituents on donor atom
- E can be part of a heterocyclic
sp3 or sp2 grouping
Fig. 1 The pincer-metal platform and the various possibilities to shape and modify it. The ECE-
pincer is potentially a six electron donor (similar to the Cp-anion)
1 Introduction
space has been studied in some detail for a series of bisamino-pincers [11] and more
extensively for the corresponding bisphosphine-pincer ligand [10].
The ECE-pincer can act as a 2e (via Cipso), 4e (via E and Cipso), or as a 6e (via all
three sites) donor ligand. A schematic representation of the pincer platform is
shown in Fig. 1. A large series of reviews is available describing the various aspects
of pincer chemistry from a variety of perspectives (e.g., [1, 6–9, 11–16]).
This chapter serves to illustrate some of the similarities and diversity of the
various pincers used in the (now) vast field of pincer-metal chemistry. Various
aspects such as the coordination properties, the synthetic routes available, the
stability and reactivity properties of pincer-metal compounds in relation to
applications as sensors and in catalysis will be touched upon with some illustrative
examples. Many of these latter aspects are playing a role in the following chapters
of this volume in which the current state of the pincer-metal chemistry in various
directions is extensively outlined.
2 Coordination Modes
Fig. 2 The coordination modes found for ECE-pincer-metal complexes in the solid state [6]
PPh3
Rh Ru La
P CO N N
Cl Cl
P N N
[32, 33]. This type of interaction is clearly observable in the trend of the catalytic
activity of NiX(C6H2(CH2NMe2)2-2,6-R-4) catalysts observed in Kharasch
reactions (i.e., the addition of halocarbons to alkenes) when the para-substituent
R in the aryl group is varied from electron donating (OMe) to electron
withdrawing (NO2) [32, 34]. However, in a similar series of para-substituted
(PCP)Ir(CO) derivatives (P¼CH2P(t-Bu)2) only a small range of CO IR stretching
frequencies is observed for a similar series of R groups [35].
In a number of studies, the para-R substituent can be used to bind ECE-pincer
metal complex to either insoluble supports or to soluble, supramolecular systems.
For example, this technique has been used to make nano-sized homogeneous
(dendritic) catalysts [9, 36, 37], or to use the ECE-pincer metal units themselves
as building blocks for the construction of supramolecular arrays [9, 38, 39].
The actual route for the synthesis of the various types of ECE0 -pincer metal
compounds depends largely on the nature of the E and E0 donor atoms. In general,
when at least one of the donor sites is a soft donor atom, direct and regioselective
biscyclometallation (route a, Z ¼ H or Br and M ¼ d8-metal) of the corresponding
arene ligand is observed. In particular, when E¼E0 ¼ –PR2 or –SR and M ¼ d8-
metal, the corresponding mer-ECE-pincer metal compound can be obtained in high
yields. Also in the case of X–E being C¼N (e.g., imine [40], oxazoline [41])
regioselective biscyclometallation can be achieved (via C–H bond activation), but
in a number of cases the oxidative addition route using C–Br bond cleavage is
required or leads to superior product yields. For most of the NCN-diamino pincer
ligands, the synthesis of the corresponding pincer metal complex requires a two-
step process involving the prior, often in situ, synthesis of the corresponding pincer
lithium reagent followed by transmetallation (route a, b in Fig. 4) [6, 42]. In order to
avoid separation problems, the bis-ortho-lithiation must be quantitative. This can be
achieved by the use of an apolar solvent and avoiding the presence of any polar or
coordinating reagent/solvent(s) in the reaction mixture, cf. the solvent dependence
of the yields of the two regioisomers in Fig. 4. As an alternative direct route,
lithiation of a bromide-pincer can be used, again followed by transmetallation. For
NCN-pincer complexes, C–SiMe3 bond cleavage has likewise been employed for
the regioselective introduction of various metal groupings to the NCN-ligand
platform [43].
Synthesis of PCP-pincer metal-d8 complexes by C–Z bond activation (e.g.,
Z ¼ OR, OSiR3, or CR3) has been demonstrated and its mechanistic details have
been studied in detail ([8], Chapter 5 in [9]).
An alternate route for pincer compounds, that are not easily accessible by other
routes, involves a transcyclometallation reaction which also affords for the selec-
tive interchange of a Cipso–H for a Cipso–M between two different ECE-pincer
platforms, see Fig. 5 [44]. This transcyclometallation protocol proved its usefulness
The Monoanionic ECE-Pincer Ligand: A Versatile Privileged Ligand Platform. . . 7
c, MHal;-LiHal
X E X E X E
a, M b, RLi
M Z Li
Z=H,Br
XE=CH2NMe2
X E' X E' X E'
XE=CH2NMe2, Z=H, Br, SiMe3
XE=CH2PR3, Z=H, Br, OR
E
E E Li
BuLi
H Li +
Et2O or
Hexane
E E E
E=NMe2 100% in Hexane 0% in Hexane
86% in Et2O 14% in Et2O
Fig. 4 Summary of some of the (cyclo)metallation routes and starting materials for the various
types of ECE-pincer ligands (top). Example of the solvent dependence of the regioselective
lithiation of NCN-pincers (below)
Fig. 5 Two alternate routes for the selective synthesis of pincer metal salts in which the difference
in coordination strength of the various donor atoms is the driving force for reaction
in the clean synthesis of, for example, dendritic structures with multiple PCP-pincer
ruthenium units [45].
Routes that make use of transmetallation via either tin or mercury intermediates
are less advantageous for environmental reasons. However, the reaction of the
8 G. van Koten
t-Bu
NPhH
O H Ph Ph
N N N
O O
N Pd N
OH
Cl
t-Bu t-Bu
OH HO
Pd(dba)3/PPh3
t-Bu
OHC CHO LiCl OHC CHO
OTf R3P Pd PR3 RNH2
Cl
RN Pd NR
Cl
corresponding pincer gold(I) derivative with even highly electrophilic metal salts
leads to the direct synthesis of the corresponding pincer metal derivative. It has
been demonstrated that the gold(I) phosphine salt that is quantitatively formed can
be recovered and recycled, see Fig. 5 [41, 46].
When more elaborate pincer metal platforms are needed, a choice can be made
between either a route in which the organic pincer ligand is synthesized first which
is then followed by the regioselective introduction of the metal grouping or an
alternate protocol involving prior introduction of the metal center followed by
functionalization of the resulting organometallic ECE-pincer metal compound.
For example, the chiral pincer palladium compound shown in Fig. 6 has been
synthesized by making first the bis-ortho-hydrocarbonylpincer palladium com-
pound (which in itself is an interesting case with monodentate-C-coordination of
the OCO-pincer ligand) followed by a condensation reaction that creates the final
ligand framework [47].
In the next step, the aldehyde groupings have been selectively converted into the
chiral ortho-scaffolds. The resulting enantiopure compound was one of the first
chiral pincer-metal complexes to be successfully used in enantioselective catalysis
[41, 47].
Further examples of postderivatization of pincer metal compounds are shown in
Fig. 7 [48]. Starting from the iodo–bromo pincer compound, a chemoselective
biscycloplatination has been carried out followed by a selective lithiation through
a lithium–iodide exchange reaction (with t-BuLi) at low temperature. Subse-
quently, the lithium–platinum pincer intermediate is quenched in situ with an
appropriate electrophile. This is the preferred route for the synthesis of materials
carrying a large number of pincer metal entities, e.g., in the case of the synthesis of
metallodendrimers for which purification procedures are cumbersome or
The Monoanionic ECE-Pincer Ligand: A Versatile Privileged Ligand Platform. . . 9
NMe2 NMe2
2 t-BuLi
I Pt Br Li Pt Br
THF; -100 oC
NMe2 NMe2
95%
[Pt(Tol)2SEt2]2
Benzene E, THF
40-90%
NMe2 NMe2
I Br E M Br
NMe2 NMe2
1, t-BuLi [Pt(Tol)2SEt2]2
2, E, Et2O NMe2 or [Pd(dba)2dba]
Benzene
80-95%
E Br
NMe2
60-90%
Fig. 7 Electrophile E is, e.g., CO2, MeSSMe, ClP(OEt)2, ClSiMe3, M ¼ Pd or Pt. Comparison of
the synthesis of para-E-NCN-pincer palladium and platinum complexes by either prior metal
introduction and then functionalization or synthesis of the complete pincer ligand and then metal
introduction (postderivatization)
N iPr
2
L Me2
N
NMe2 M M = Ir(I), R = Me or CH2NMe2, XL = COD
X
D M = Ru(II), R = CH2NMe2, X = h5- Cp, L = PPh3
M L M = Ru(II), R = CH2NMe2, X = Cl, L = h6- p-cumene
Benzene
MXL = Ta(V)Cl(Ot-Bu)(=Ct-Bu), R = CH2NMe2
R X R
L Me CH2D
Me N
D N Me Ir
60 °C
L
D Ir L D LL = COD
Benzene
D R L D R
the Pd NPs) will ultimately also affect the size and constitution of the NPs by
absorbing onto their surfaces. Consequently, this interaction can be expected to
affect the aggregation rate of these particles as well as the activity of the Pd(0)
species at the surface in subsequent catalytic cycles.
In the above-mentioned reactions, it is the cleavage of the M–Cipso bond that is
the cause for the (controlled) decomposition of the ECE-pincer metal compound at
higher temperatures. This (homolytic) bond cleavage leads to destruction of the
pincer metal platform. However, loss of the unique stability and reactivity
properties of the ECE-pincer metal motif can also occur as a result of selective
rearrangement of the bis-ortho-E, C, E arrangement to an ortho-E, para-E, C one.
In addition to the decomposition by homolytic C–M bond cleavage, occurrence
of this selective rearrangement is of particular importance when ECE-pincer metal
compounds are used as catalysts or, for example, in sensor devices. So far, these
rearrangements have been observed for NCN-diamino pincers if the metal is Ir(I)
[55], Ru(II) [56], or Ta(V) [57], again emphasizing the importance of the nature of
the donor atoms E. In Fig. 9 a number of the observed rearrangements are
summarized. The observed rearrangement of the pincer anion from the bis-ortho-N,
Cipso, N arrangement to an ortho-N, para-N, Cipso could be extensively documented
by model experiments and selective deuterium-labeling protocols. With all three
metals, this rearrangement was kinetically driven by the fact that in the final ortho-
N, para-N-isomer, the other ortho-position next to the Cipso-metal bond is occupied
by a C–H functionality rather than a free, sterically demanding CH2NMe2-group-
ing, as would be the case in the bis-ortho chelated-isomer. This makes the C–H
activation and subsequent oxidative addition processes irreversibly running
towards the formation of a thermodynamically most stable isomer. It must be
noted that these processes occur intramolecularly and provide almost quantitative
yield of the rearranged product. For the NCN-pincer Ir COD compound, the result
12 G. van Koten
Me2HN+
I O O
S
I NMe2 I
Pt I Pt
NMe2 NMe2 I
Pt I
NMe2 SO2-sensor
2
Me2HN+
-SO2 SO2, X=I
X=I I2 K=0.1 HI
Cl Cl2 MeI
Pt Cl Pt X Pt I
X=Cl MeX
Cl
NMe2 NMe2 NMe2
Pi-Pr2 Pi-Pr2
[RhCl(C8H14)2]2
+ H-R Me-R +
D
Pi-Pr2 Pi-Pr2
R=H, Si(OEt)3
During the past two decades, the pincer metal platform is increasingly used as a
homogeneous (pre-)catalyst in organic synthesis and as a building block in supra-
molecular chemistry. This successful use of the pincer motif as a privileged ligand
derives from the fact that the M–Cipso bond of many ECE-pincer metal compounds
appears to be relatively unreactive. In addition, because of its compact size and
flexible and versatile bonding properties, the pincer ligand leaves a number of well-
defined coordination sites and space available for other reactivity. Small molecules
that are commonly used in homogeneous catalysis coordinate and react at the metal
site of the pincer metal platform without interfering with the M–Cipso bond. For
example, reactions with CO yield CO complexes, whereas complexes with a similar
binding set of monodentate ligands would readily undergo insertion chemistry to
yield the corresponding acyl complexes. Similarly NCN-pincer platinum
compounds bind reversibly SO2 (in solution [65] and in the solid-state [66])
yielding the corresponding Z1-SO2 coordination complexes (see Fig. 11) rather
than yielding the otherwise expected SO2-insertion products. Most interestingly,
s-coordination of CH4 to the Rh center of PNP pincer Rh complexes has been
recently documented [67].
Reactions with molecular hydrogen yield initially the H2-coordination
complexes and subsequently hydride derivatives. In many cases, the pincer-metal
platform shows surprising stability toward reductive elimination of the hydride with
Cipso that would otherwise lead to formation of the arene pincer, i.e., would lead to
destruction of the catalyst [cf. 21, 55]. An interesting example is the reaction of
PCP-(e.g., bis-phosphine [68] and bis-phosphinite [69]) pincer Ir complexes with
alkanes that yield alkenes via dehydrogenation (cf. the s-coordination of CH4
mentioned earlier). Crucial in these reactions is the stability of the incipient ECE-
pincer Ir manifold in the Ir-hydride intermediates towards decomposition (via
Cipso–H bond formation). An PCP-pincer Ir catalyst with considerable stability is
shown in Fig. 13 that also visualizes the application of immobilization of homoge-
neous pincer catalysts on solid supports [70].
These heterogenized pincer catalysts combine the advantage of homogeneous
(high reactivity and selectivity) catalysis with those of their immobilized analogues
(easy separation of the catalyst from products) as was first demonstrated for
dendritic NCN-pincer Ni catalysts [36].
The Monoanionic ECE-Pincer Ligand: A Versatile Privileged Ligand Platform. . . 15
OK
O O
(t-Bu2)P Ir P(t-Bu2)
+ +
Fig. 13 Example of a highly active and recyclable (immobilized on g-alumina) PCP-Ir catalyst
for transfer dehydrogenation of alkanes
The actual composition of the pincer platform affects both the reactivity and the
thermodynamic stability of the pincer metal manifold particularly with respect to
the formal oxidation state of the metal. An early observation represents the isolation
of stable, paramagnetic NCN-pincer Ni(III)Br2, see Fig. 14, from the reaction of
NCN-Ni(II)X with X2.
The facile and selective oxidation of the NCN Ni(II) to the corresponding Ni(III)
complex pointed to the effect that the strong s-donating NMe2 groupings have on
the NCN d8-metal manifold in facilitating oxidation of the metal and hence stabili-
zation of the resulting higher oxidation state. NCN-Ni(III)X2 is both water and
air-stable whereas related NCN-Ni(II)X oxidizes readily under these conditions to
the Ni(III) species [34, 36, 37, 71]. Likewise, the presence of stabilizing ortho-
phosphine ligands allows for the synthesis of thermally stable low valent platinum
species Na[PCP-Pt(0)] [21, 72]. Relatively rare NCN-pincer Rh(II) species (NCN is
“benbox”) were isolated from the reaction of RhCl3(H2O)3 with the corresponding
benbox arene precursor via C–H bond activation. The complex is a paramagnetic
species with a S ¼ 1/2 ground state. These Rh(II) species are thermally unstable
and disproportionate via a complex reaction scheme [73]. Following the early
synthesis of NCN-pincerSn(II)R (R¼Cl, p-tolyl) compounds [74], a whole series
of pincer compounds were isolated and characterized having a variety of ECE0 -
pincer ligands [75]. Interestingly, reduction of the Sn(II) compounds with K
[HBEt3] afforded, instead of the desired NCNSn(II) hydride, the unusual
distannyne NCNSn(I)Sn(I)NCN [76].
Until several years ago, all stable (isolated and characterized) organocopper
compounds were copper(I) species [77], whereas organocopper(II) and (III) species
were frequently postulated as reaction intermediates and/or transient species. This
is also true for the few known pincer copper compounds, e.g., [N0 NCNN0 Cu
(I)2]2[Cu(I)Br3], see Fig. 3 [29]. This situation changed entirely when researchers
started to use macrocyclic pincer type ligand platforms [78–80]. NCNCu(III)X2 is a
representative of new and exciting chemistry that afforded both stable and isolable
16 G. van Koten
NMe2 Na
P(t-Bu)2
Ni X Pt
X
NMe2 P(t-Bu)2
NCN-Ni(III)X2
PCP-Pt(0)
H O
R
N (CH2)n
N R'
X Cl
Rh
Cu N Cl
X N R'
N
R
H O
NCN-Cu(III)X2 NCN (benbox)-Rh(II)X2
Fig. 14 Four complexes with the metal center in uncommon formal oxidation state
P(t-Bu)2
P(t-Bu)2 Rh Cl
(RhCl(C8H14)2]2 P(t-Bu)2
OH
P(t-Bu)2 +
(t-Bu)2P
P(t-Bu)2
Cl Rh
O
O
Rh Cl
(t-Bu)2P
P(t-Bu)2
NMe2 X2
X Ru(Terpy)
NMe2
NMe2
2 Cu(II)X2
Ru(Terpy)
- 2 Cu(I)X + X4
Me2N NMe2
NMe2
Me2N NMe2
Ru(III)Ru(III)
Fig. 15 Two reactions involving oxidative conversion of the pincer metal platform
8 Conclusion
Initially the pincer ligand motif, see Fig. 1, had been considered as a interesting
monoanionic, terdentate ligand but with seemingly simple structural features. Since
that time however (35 years later), its successful application in organometallic
chemistry, materials and catalysis science has led to fascinating and novel chemis-
try and many unprecedented results. Many of these discoveries are a demonstration
of the subtle interplay that occurs in these pincer-metal compounds between the
monoanionic pincer ligand and metal center; it has given the pincer ligand motif the
status of privileged ligand in organometallic chemistry that it features nowadays.
Moreover, in many aspects the properties and structural features of the pincer
ligand complement those of the unique cyclopentadienyl anion.
In recent years, novel pincer ligands have been developed, see Fig. 1, different
connections X now representing, for example, (CH2)n (n is e.g., 1 or 2), NH, or O
and in which the anionic ligand site is not C but is a monoanionic N- or P-center
18 G. van Koten
resulting in a central covalent M–N and M–P bond, respectively. Moreover, rather
than having similar flanking ligands pincer platforms with two different ligand arms
flanking the central covalent bond have been developed, cf. [84]. The understanding
of the way these changes of the pincer platform affects both the structural features
of the resulting pincer metal complexes and their reactivity is only at its beginning.
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Top Organomet Chem (2013) 40: 21–48
DOI: 10.1007/978-3-642-31081-2_2
# Springer-Verlag Berlin Heidelberg 2013
Abstract Pincer complexes are generally viewed as stable compounds in which the
pincer ligand framework remains unchanged during stoichiometric and catalytic
reactions. However, there are now several cases in which the pincer ligand itself
undergoes transformations that result in extraordinary reactivity of the metal com-
plex and formation of unusual species. In the current chapter, we review our work on
“noninnocent” reactivity modes of various PCP and PCN-type pincer ligands of Rh,
Ir, Ru, Os, Pd, and Pt. Participation of the arene ring in the reactivity of PCP type
complexes has led to formation of unprecedented quinonoid complexes, including
complexes in which the pincer ligand adopts structures of quinone methides, thio-
quinone methides, xylylenes, methylene arenium, and oxo-arenium compounds. In
addition, pincer systems can collapse and be regenerated under redox conditions,
and reduction can lead to a ring-localized radical anion complex. The generation of
C–H agostic arene PCP complexes has led to new insights regarding the C–H bond
activation process, and the effect of CO ligands on it.
Keywords Pincer ligands, xylylene complex, quinone methide complex,
thioquinone methide complex, phenoxonium complex, methylene arenium
complex, agnostic pincer complex, late transition metals, reactive intermediates
Contents
1 Introduction and Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2 Arene System Perturbation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.1 Quinone Methides and Quinonoid Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2 Phenoxonium Cation Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.3 Self-Oxidation of a Phenolate Complex to a Bimetallic Stilbene Quinone . . . . . . . . . . 27
2.4 s-Coordinated Naphthyl Radical Anion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3 Agostic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.1 sp3 C–H and sp2 C–H Agostic Ruthenium Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.2 Unexpected Role of CO in C–H Oxidative Addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4 Collapse and Regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4.1 Redox Induced Collapse and Regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4.2 A Pincer-Type Anionic Pt(0) Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
5 Hemilabile Pincer-Type PCN Ligand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.1 Anionic Complexes Based on a Hemilabile PCN Ligand . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Scheme 1 Formation of the rhodium quinone methide complex 1 based on a PCP ligand
S PtBu2
H3CO PS
SP OCH3 S Rh Cl
S
Lawesson's reagent PtBu2
2
PtBu2
PtBu2 PtBu2
O Rh Cl
2 MeLi Rh Me
1 PtBu2
Rh Me +
PtBu2 PtBu2
3 4
ROTf OTf -
PtBu2
RO + Rh Cl
PtBu2
5
Quinone methides (QMs) are quinones in which one oxygen atom has been
replaced by an alkylidene group. They are highly reactive compounds which
participate in many chemical and biological processes ([33–35] and references
therein), such as formation of substituted phenols [36], Diels–Alder reactions
[37], biosynthesis of the natural polymers [38–40], and radical scavenge [41, 42].
Quinone methides are also able to react with functional groups of biopolymers,
such as DNA and proteins, and several drugs are believed to generate QM moieties
as an active form [43, 44].
Quinone methides, especially the simple ones (those not having substituents at
the exocyclic methylene group) are very unstable compounds and their isolation is
seriously obstructed or requires extremely diluted solutions and low temperatures
[45]. Being a highly polarized molecule, QMs rapidly react with both nucleophiles
and electrophiles and easily convert to their bi-radical triplet form, opening up
several additional reactivity patterns.
24 E. Poverenov and D. Milstein
Scheme 3 Formation of osmium quinone methide complexes, 6 and 7, based on a PCP ligand
R R
O -
O
+
[M]
R [M] R
+
+ O M
O O O
M
+ +
R R R R
A B A' B'
Scheme 7 Formation of iridium phenoxonium complexes, 11 and 11a, based on PCP ligand
Fig. 1 ORTEP view of complex 11a at 50 % probability. Hydrogen atoms are omitted for clarity.
Bond lengths (Å): Ir1-O6 2.061, Ir1-C6 2.189, C6-O6 1.356, C6-C11 1.432
charge is localized at the ortho and para positions, the corresponding carbon atoms
show a 20–40 ppm downfield shift compared with the neutral complex. Addition of
acetonitrile to a solution of 11 resulted in a CH3CN adduct 11a (Scheme 7).
Noninnocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes 27
The X-ray structure of 11a (Fig. 1) reveals a quinonoid compound in which the
exo-cyclic double bond is Z2-coordinated to the metal center. The long C–O bond
(1.356 Å) indicates considerable back bonding from the metal center. The X-ray
structure shows that all six carbon atoms are located in the same plane, with the
coordinated oxygen atom pushed out of the plane by approximately 10 .
Isolation and characterization of complexes 11 and 11a confirmed the postulated
A0 ! B0 process. While Z2 metal complexation to a C¼C double bond is well
known, no examples of such coordination to C¼O bonds in quinonoid compounds
have been reported. Complexes 11 and 11a are, therefore, the first examples of
metal-stabilized phenoxonium compounds.
1) [RhCl(C8H14)2]2
PtBu2 tBu2P
2) Ag2O3 PtBu2
O
OH Cl Rh O
Rh Cl
PtBu2 tBu2P
PtBu2
12
Fig. 2 An ORTEP diagram of complex 12 at 50 % of probability. Hydrogen atoms are omitted for
clarity. Selected bond lengths (Å) and angles ( ): Rh(1)-O(6) 2.056, Rh(1)-C(5) 2.186, Rh(1)-Cl(2)
2.316, Rh(1)-P(3) 2.329, Rh(1)-P(4) 2.346, C(5)-O(6) 1.325, C(13)-C(14) 1.395, C(14)-C(14A)
1.404; P(3)-Rh(1)-P(4) 167.84
[MCl(C8H14)2]2 PtBu2
PtBu2 PtBu2
M = Rh, Ir O M = Rh
OH M Cl Rh Cl + 12
H
t
P Bu2 PtBu2 PtBu2
13, M = Rh 14
15, M= Ir
Scheme 9 Reactivity of rhodium and iridium precursors with a phenol-type pinder ligand,
resulting in case of Rh(I) in C–O cleavage and oxidative coupling
K+
P
P P P
H2O 16 + Rh H2
K -.
Rh N N Rh Rh
[Cp2Fe][BF4] P
P P - H2 P
- KOH
16 radical anion 18
17
Scheme 10 Formation of complex 17 by reduction of 16 with potassium metal and its reactivity
towards water and ferrocene tetrafluoroborate
Aromatic radical anions have been extensively studied, involving structural, physi-
cal, theoretical, and reactivity aspects, and have found many applications [78–80].
They show interesting reactivity toward a variety of substrates such as alkanes,
alkenes and alkynes, aliphatic and aromatic halides, silyl halides, aldehydes and
ketones, sulfur dioxide, sulfonates and sulfonamides, carbon dioxide, dihydrogen,
dinitrogen, as well as aliphatic and aromatic esters. An example for synthetic use is
the reductive metalation of phenyl thioethers [81, 82], providing a useful route to
the preparation of organo-alkali compounds difficult to prepare by other routes,
such as tertiary organolithium compounds [83]. It occurred to us that it might be
possible to generate a pincer-type radical anion complex.
The binuclear Rh pincer complex 16, bearing an s-bound naphthyl system, was
utilized to generate an organometallic radical anion [84]. Formation of a stable
radical anion by reduction of naphthalene is well known [78–80, 85]. Treatment of
16 with potassium metal in THF resulted in a new, NMR silent product, while EPR
measurements gave rise to a strong, complex signal revealing formation of the
paramagnetic anion radical complex 17 (Scheme 10).
The EPR signal of 17 has a g value of 2.0035, typical for aromatic hydrocarbon
radicals (Fig. 3). The magnetic susceptibility of 17 was also measured by the Evans
NMR method at 298 K in THF, giving a magnetic moment of 1.68 mB and
confirming the presence of a single electron.
While the electron is localized in the naphthyl unit, reactivity of complex 17 is
strikingly different from that of the naphthide radical anion (Scheme 10). Thus,
when a THF solution of the reduced complex 17 was treated with water, immediate
evolution of dihydrogen, with almost quantitative re-oxidation to the starting
complex 16, took place. A small amount (~10 %) of the dihydrogen complex
(C10H5(CH2PiPr2)2)Rh(Z2-H2) (18) was also formed, as a result of the reaction of
16 with H2, as confirmed by the independent synthesis of 18. No ligand protonation
30 E. Poverenov and D. Milstein
3 Agostic Systems
t +
AgX Bu2 X-
Pt Bu2 1) RuCl3· 3H2O Pt Bu2 P CO
MeOH, Et3N, D (X = BF4-, PF6-, BPh4-)
CO Ru CO
Ru CO
2) CO, 1 atm, r.t. - AgCl P H
Cl t
Bu
Pt Bu2 Pt Bu2 19 CH2
H3C
CH3
Fig. 4 ORTEP drawing of the molecular structure of 19 showing the agostic CH Ru(II)
interaction. Thermal ellipsoids are drawn at 50 % probability
were isolated and fully characterized, including rhodium [96], iridium [97], and
ruthenium [98–101] complexes based on cyclometallated bisphosphine ligands
having tert-butyl or aryl substituents on both phosphorus donor atoms [2]. Herein,
we present several examples of stable agostic complexes based on PCP pincer
ligands.
As we observed, alkyl and aryl agostic interactions can occur in similar steric and
electronic environments [102]. Halide abstraction from the 18 electron Ru(II)
32 E. Poverenov and D. Milstein
t +
Bu2 X- t
Bu2
P CO P H Pt Bu2
H2 H Ru CO CO
Ru CO Et3N
Ru CO
t
P H P CO
Bu t
H
19 CH2 Bu2 - [Et3NH]X
20 21 Pt Bu2
H3C
CH3
Scheme 12 Transformation of 19 to an sp2 C–H agostic complex 20 and formation of the neutral
complex 21
1.5
0
Relative Energy (kcal/mol)
–5
–4.6
–10 –8.5
–9.5
–15
–14.5
–20
–23.0
–25
19* 22* TS (22*-20*) 20*
Fig. 5 Geometries of the calculated structures and the reaction profile. The energies are relative to
19* + H2. The curve in blue is DEe while the red curve is DG298 (atomic color schemes: C, brown;
H, white; Ru, gray; O, red)
extent that complex 20 was deprotonated with Et3N to form the neutral complex 21
(Scheme 12).
The 19 ! 20 transformation, involving both C–H bond formation and activa-
tion, has been mapped out in detail using DFT calculations (Fig. 5). The addition of
H2 to agostic 19* leading to the s-H2 complex 22* is exergonic (DG298 ¼
3.6 kcal/mol). Complex 22* is octahedral and has the “nonclassical” dihydrogen
ligand aligned parallel to the Ru–Cipso bond. The next step of H transfer from H2 to
the aromatic ring to give 20* is also exergonic (DG298 ¼ 5.9 kcal/mol). In
complex 20* the aromatic ring is dramatically bent relative to the metal plane of
coordination (Ru–Cipso–Cpara ¼ 111.8 ). The interaction with the ruthenium center
is apparent from the elongated C–H bond (1.092 Å vs. 1.088 Å) and the bending of
this H from the aromatic plane (H–Cipso–Cpara ¼ 165.9 ). The transition state
TS (22*–20*) has a reaction barrier of DG298{ ¼ 5.1 kcal/mol and a reverse
reaction barrier of DG298{ ¼ 11.0 kcal/mol. These values are consistent with the
observed hydrogen addition and fluxional behavior of the system. It should be noted
that a Ru(IV) dihydride intermediate is not observed. Thus, this H–H activation is
better classified as an s-bond metathesis rather than an oxidative addition reaction.
The formation and reactivity of complexes 19 and 20 demonstrate the ease by
which cycloruthenalated ligand systems undergo reversible two electron, three
center CH Ru interactions. It is also noteworthy that the cyclometalated
Ru–Caryl s-bond can be formed and activated under very mild reaction conditions.
According to the classic work of Saillard and Hoffmann [103], oxidative addition of
a C–H bond to a transition metal center involves a two-way electron transfer (from
the filled s orbital of the C–H bond into an empty metal d orbital, and from a filled
metal d orbital into the empty s* orbital of the C–H bond). Overall, this process
produces net electron density transfer from the metal to the C–H bond (which splits
into formally anionic hydrocarbyl and hydride ligands). Therefore, the presence of
electron-withdrawing ligands, such as the strong p-acceptor ligand carbon monox-
ide, would be expected to hinder oxidative addition and to facilitate reductive
elimination of C–H bonds by lowering the electron density at the metal center
[104–106].
Our studies with a series of pincer-type bisphosphine cationic rhodium
complexes yielded intriguing observations regarding the effect of CO on the
activation of C–H bonds [107, 108]. When the Rh(III) aryl-hydride complex 23
was treated with one equivalent of CO, facile C–H reductive elimination took place,
as expected, to yield the agostic Rh(I) complex 24 (Fig 6) [107]. Surprisingly, when
a second equivalent of CO was added to this system, facile oxidative addition of the
same C–H bond took place, yielding the Rh(III) aryl-hydride complex 25
(Scheme 13). Both experimental and theoretical evidence indicated that this
34 E. Poverenov and D. Milstein
Fig. 6 Crystal structure of complex 24. Selected bond distances (Å) and angles ( ):
Rh-Cipso ¼ 2.267, Rh-H ¼ 1.97, Rh-P1 ¼ 2.321, Rh-P2 ¼ 2.327, Rh-CO ¼ 1.816, C–O ¼ 1.153,
Cipso-Rh-P1 ¼ 83.491, Cipso-Rh-P2 ¼ 83.78, Cipso-Rh-H ¼ 23.90, CCO-Rh-P1 ¼ 96.09, CCO-Rh-
P2 ¼ 96.61
oxidative addition reaction was actually promoted by CO, which did not merely act
as a trapping agent.
Formation of complex 25 is unexpected. The agostic complex 24 is by itself an
electron-poor system, as judged by the low Rh-P coupling constant (99.3 Hz), and it
is quite counter intuitive that the addition of a second equivalent of CO to 24 (which
is expected to further diminish the electron density at the metal center), actually
results in the oxidative addition of the same C–H bond. Nevertheless, this reaction
was found to be highly reversible and CO dependent. The reversibility of the
reaction was clearly evident by NMR measurements that demonstrated scrambling
of labeled 13CO in complex 25 and a dynamic equilibrium of 24 $ 25 as indicated
by spin saturation transfer (SST). In light of these observations it is reasonable to
assume that the reaction leading from 24 to 25 involves two elementary steps: C–H
cleavage and CO coordination. Consequently, two alternative mechanistic path-
ways were proposed, as shown in Scheme 14. Pathway A involves direct oxidative
Noninnocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes 35
+ BF4-
P(iPr)2
Rh CO
CO
A H P(iPr)2
-C A
+ BF4- 26 O + BF4-
P(iPr)2 P(iPr)2
H
Rh CO Rh CO
CO
P(iPr)2 H P(iPr)2
24 25
CO
-C
O
B B
-
+ BF4
P(iPr)2
H
Rh CO
P(iPr)2
27
addition of the agostic C–H bond to yield the square-pyramidal intermediate 26,
which then undergoes trapping by CO to afford complex 25. Pathway B initially
involves coordination of a CO ligand to complex 24, yielding trigonal-bipyramidal
(TBP) intermediate 27, followed by cleavage of the arene C-H bond.
The unknown complexes 26 and 27 could not be detected. Therefore, DFT
calculations were employed in order to investigate the systems described in
Scheme 14. A priori, pathway A was assumed to be more probable than B, since
the monocarbonyl complex 24 is expected to be more electron-rich than the
dicarbonyl intermediate 27 and hence appears more likely to undergo oxidative
addition of the C–H bond (24 ! 26). Moreover, the fact that 24 is an agostic
complex made it a very reasonable candidate for C–H bond cleavage, since such
complexes are widely accepted as precursors of C–H activation. Therefore, it was
rather surprising to learn that the DFT calculations yielded very different results.
Not only did they suggest that both pathways are possible, but the CO-promoted
oxidative addition (pathway B) was found to be more favorable. Intermediate 27
was calculated to be 9.0 kcal/mol more stable than 26, and even more stable than 24
by 1.2 kcal/mol. Strong experimental support for the involvement of intermediate
27 in the formation of complex 25 came from the observation that upon mixing the
cationic RhI precursor [Rh(CO)2(acetone)2]BF4 with the PCP ligand 1,3-bis((di-
iso-propylphosphino)methyl)benzene in 1:1 ratio in acetone, complex 25 was
obtained (as indicated by NMR at 55 C), with no significant amounts of complex
24 being observed. These results show that complex 25 can be produced by a direct
reaction between the PCP ligand and a cationic RhI-dicarbonyl fragment.
36 E. Poverenov and D. Milstein
Fig. 7 ORTEP diagram of a molecule of 29, showing the atom labeling scheme (50 % proba-
bility). Hydrogen atoms are omitted for clarity. Selected bond distances (Å) and angles ( ):
Pd1-P4 ¼ 2.288, Pd1-P2 ¼ 2.295, Pd1-Pd2 ¼ 3.039, Pd2-P3 ¼ 2.245, Pd2-P1 ¼ 2.250; P4-
Pd1-P2 ¼ 144.82, P3-Pd2-P1 ¼ 170.48
In addition, a rare agostic C–C complex of Rh based on the PCN ligand was
demonstrated. In this system a remarkable degree of control over C–C vs. C–H
bond activation was reached by choice of rhodium precursor [109].
1
We are aware of two examples of completely nonplanar (rather than distorted square planar)
Pd(II)L4 complexes, only one of them being diamagnetic [112, 113].
Noninnocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes 37
AgOTf
PiPr2 P
Na P
Pd Cl 1/2 Pd Pd
-NaCl P
P
28 PiPr2 29
RX R = Ph; X = I
R = PhCH2; X = Cl
-R-R
Upon reaction of the (PCP)Pd(II) complex 28 with sodium in THF, two new
signals with the same intensity at d 55.89 and 36.96 ppm were observed in the
31
P{1H}NMR spectrum, suggesting formation of a binuclear complex. An X-ray
diffraction study revealed that a new binuclear palladium complex 29 was formed,
incorporating a very rare, nonplanar diamagnetic Pd(II)1 center and a 14e Pd(0)
center (Fig. 7). The solid state structure of 29 exhibits a 4-coordinate Pd(II) center
with a distorted butterfly geometry and a Pd(0) center linearly complexed by two
phosphine arms from different PCP ligands. The short PdðIIÞ Pdð0Þ distance
(3.039 Å) suggests that the extremely rare butterfly arrangement of the Pd(II) center
with almost linearly coordinated phosphine arms is probably a consequence of
steric effects and the rigidity of the PCP ligands.
Remarkably, the original PCP Pd(II) mononuclear framework can be
regenerated upon direct oxidation of the binuclear complex or upon its reaction
with organic halides. Thus, when complex 29 was treated with an excess of benzyl
chloride, immediate quantitative formation of the monomeric PCP–Pd–Cl complex
was observed and dibenzyl was detected by GC. Similarly, addition of iodobenzene
to a THF solution of complex 29 led to formation of the PCP–Pd–I complex and
biphenyl but at a much slower reaction rate. These reactions likely indicate electron
transfer from the Pd(0) center to the organic halide.2 Supporting the electron
transfer reaction, addition of two equivalents of AgOTf to a THF solution of 29
resulted in immediate and clean formation of the monomeric PCP–Pd–OTf com-
plex as well as silver metal (Scheme 15).
Although mechanistic studies were not performed, a possible scenario for
formation of 29 might include a single electron transfer from Na to Pd(II) with
precipitation of NaX and formation of a tri-coordinated Pd(I) intermediate which is
2
A mechanism involving organic halide oxidative addition to generate dibenzyl or biphenyl is also
possible. See, for example [114].
3
In analogy to nonchelating systems, where reduction of PtCl2L2 (L ¼ bulky tert-phosphines)
with Na/Hg in THF affords PtL2 complexes, while reduction of PdCl2L2 (L ¼ bulky tert-
phosphines) with Na/Hg in THF resulted in formation of metallic palladium. The reduction was
achieved only when excess phosphine was used. See [116] and references therein.
38 E. Poverenov and D. Milstein
P(t-Bu)2
H2O (D2O)
Pt H(D)
-NaOH(D)
2[FeCp2][BF4] P(t-Bu)2
Scheme 16 Formation and reactivity of anionic Pt(0) complex, 30 based on PCP ligand
Pt Pt
A P(t-Bu)2 B P(t-Bu)2
4
For nonisolated, anionic palladium(0) intermediates, and their involvement in oxidative addition
reactions, see [119, 120].
Noninnocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes 39
P(t-Bu)2
NMe2
Complex 30 acts as a Br€onsted base and endures protonation by water to give the Pt
(II)-H complex, and as an efficient electron transfer reagent, being reoxidized
quantitatively to Pt(II). It is capable of activation of the strong C–F bond of
hexafluorobenzene even at 35 C (Scheme 16).
The planar T-shaped geometry proposed for 30 based on NMR spectroscopy is
supported by DFT calculations. The computational study also indicates that the
negative charge is localized mostly at the metal center of the anionic complex 30
(Structure A), rather than delocalized between the metal center and the s-bound
aryl backbone (Structure B) (Scheme 17) .
We are aware of only one monometallic anionic Pt(0) complex, [Pt(Me2NCS2)
(PEt3)], which was generated in situ at 78 C, by proton abstraction from the Pt
(II) hydride complex [PtH(Me2NCS2)(PEt3)] [117, 118]. This complex was not
isolated but rather trapped with variety of electrophiles giving a range of Pt(II)
complexes [117].4
The hardness of the chelating N donor in NCN-type ligands vs. softness of P donor
in the PCP system results in very different behavior of the corresponding NCN and
PCP based complexes. While each of these systems has its own unique chemistry,
the mixed PCN ligand benefits from advantages of both systems, demonstrating
remarkable chemistry including exclusive C–C [47], C–H [47, 109], and catalytic
C–N [121] bond activation. The different donor properties and more labile coordi-
nation of the amine “arm” in comparison to the phosphine [122] open up additional
reactivity patterns. A more flexible complex with effective hemi-labile coordination
could render the complex more adaptable to the different electronic, steric, and
coordination requirements of different steps of a catalytic cycle, or to different
stoichiometric reactions. In order to enhance the hemilability, a new PCN ligand
with a longer amine “arm” was synthesized (Fig. 8), and utilized as described below.
40 E. Poverenov and D. Milstein
- Li+
P(t-Bu)2 MeLi P(t-Bu)2
MeLi
Pt Me Pt Me
Me
P(t-Bu)2 N N
Pt Cl
32
- Li+
N
PhLi P(t-Bu)2 P(t-Bu)2
PhLi
31 Pt Me Pt Ph
Ph
N N
33
Scheme 18 Formation of the anionic “open arm” dimethyl and diphenyl Pt complexes 32 and 33,
based on “long arm” PCN ligand
- Li+ I
P(t-Bu)2 P(t-Bu)2
Pt Me Pt Me +
Me H2 O CH4
N N
32 CH3I CH3CH3
Scheme 19 Reactivity of the anionic complex 32 with electrophiles, resulting in “arm closure”
Anionic transition metal complexes are of interest due to their nucleophilic reactivity
toward organic molecules ([123] and references therein) and their utilization in the
preparation of homo- and heteronuclear transition-metal clusters [124]. Usually,
these complexes are stabilized by electron-acceptor ligands, which allow
delocalizing of the electron density at the metal center. For instance, various
anionic complexes containing carbonyl (for examples, see [125, 126]), olefin (for
examples, see [127] and references therein) and PR3 (R ¼ F, OR, Me) [128–131]
ligands were reported. However, since delocalization of charge density decreases
the reactivity of such complexes toward electrophilic reagents, formation of rela-
tively stable anionic complexes in the absence of strong electron accepting ligands
is desirable, but relatively few examples of such compounds are known (for
examples, see [107, 132]). Utilizing the hemilability of the “long arm” PCN ligand,
a series of Pt(II) anionic complexes that bear no electron withdrawing ligands and
exhibit relative stability and reactivity toward electrophiles were prepared.
Noninnocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes 41
- Li+
P(t-Bu)2 P(t-Bu)2 Et BHLi P(t-Bu)2
Et3BHLi 3
Pt Cl Pt H Pt H
MeI / H2O H
N N - CH4 / H2 N
31 34 35
Upon reaction of the “long arm” pincer Pt complex 31 with two equivalents of
methyllithium, the anionic dimethyl Pt(II) complex 32 was formed and was fully
characterized by NMR spectroscopy and X-ray single crystal analysis (Scheme 15).
According to the 1H and 13C{1H} NMR data, the amine “arm” of the PCN ligand is
not coordinated to the metal center, since the methyl groups of NMe2 exhibit a
single resonance without Pt satellites. It is likely that Li+ is coordinated to the
nitrogen of the dissociated amine “arm,” contributing to the stability of the anionic
complex. The same mode of reactivity was observed with other organolithium
compounds. Thus, reaction of 31 with a stoichiometric amount of phenyllithium
led to formation of the mono-phenyl Pt(II) complex, while addition of two
equivalents of PhLi to 31 gave the anionic diphenyl Pt(II) complex 33 (Scheme 18).
The anionic complexes are highly reactive with various electrophiles, thereby
regenerating the pincer framework (Scheme 19). For example, reaction of 32 with
MeI led to formation of the monomethyl neutral complex and ethane. Likewise,
reaction of 32 with H2O led to immediate formation of the monomethyl neutral
complex and methane. Moreover, complex 32 is capable of reaction even with
weak electrophiles such as iodobenzene or bromobenzene leading to monomethyl
neutral complex and toluene. This reaction was slower than the reactions with MeI or
water and quantitative formation of monomethyl neutral complex was observed only
after 24 h.
The hemilability of the amine “arm” of the PCN ligand, enabled the preparation of
the first anionic d8 platinum dihydride complex, via direct nucleophilic attack on
the metal center. Thus, upon reaction of complex 31 with one equivalent of
Et3BHLi, the expected monohydride complex 34 was formed, while using an
5
Very unstable, not isolated [144].
42 E. Poverenov and D. Milstein
P(t-Bu)2
Pt Me
- Li+ MeI
P(t-Bu)2 P(t-Bu)2 P(t-Bu)2 N
Et3BHLi MeLi - CH4
Pt Cl Pt H Pt H
THF THF CH3 P(t-Bu)2
N N N H2O
Pt H
31 34 36 - CH4
N
excess of Et3BHLi resulted in the novel anionic dihydride complex 35 (Scheme 20),
which was fully characterized, including an X-ray structure (Fig. 9). Similarly to
the anionic dialkyl and diaryl complexes, 35 is highly reactive with electrophiles.
For example, it reacts readily with water and methyl iodide at room temperature,
resulting in immediate formation of the monohydride complex and H2 or methane,
respectively.
Noninnocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes 43
- - -
P(Me)2 PMe2 PMe2 PMe2
H2O -CH4
Pt H Pt H2 Pt H Pt H
-LiOH
Me Me CH4
36 N N N N
6 Conclusions
References
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coordination chemistry II, vol 6, 2nd edn. Elsevier, Oxford, pp 673–745
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130. Watson PL, Muetterties EL (1978) J Am Chem Soc 100:6978
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133. Poverenov E, Gandelman M, Shimon LJW, Rozenberg H, Ben-David Y, Milstein D (2004)
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13:1991–1999
135. Shilov AE, Shul’pin GB (2000) Activation and catalytic reactions of saturated hydrocarbons
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137. O’Reilly SA, White PS, Templeton JL (1996) J Am Chem Soc 118:5684–5689
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140. Iron MA, Lo HC, Martin JML, Keinan E (2002) J Am Chem Soc 124:7041–7054
141. Wick DD, Goldberg KI (1997) J Am Chem Soc 119:10235–10236
142. Stahl SS, Labinger JA, Bercaw JE (1995) J Am Chem Soc 117:9371–9372
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Top Organomet Chem (2013) 40: 49–88
DOI: 10.1007/978-3-642-31081-2_3
# Springer-Verlag Berlin Heidelberg 2013
Dean M. Roddick
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2 Phosphine Pincer Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.1 Benzylic PCP Pincers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.2 Resorcinol-Based POCOP Pincers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
2.3 PENEP Pincers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3 Pincer Sterics, Conformation, and Coordination Geometries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.1 Pincer C2 Twist Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.2 P–M–P Angle Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3 5-Coordinate Pincer Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.4 d8 5-Coordinate Pincer Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.5 Nonmeridional Complexes and Reaction Intermediates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4 Phosphine Pincer Electronic Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
4.1 n(CO) Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
4.2 Electrochemical Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
4.3 Reactivity and Coordination Affinity Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
1 Introduction
The original tBuPCPH pincer synthesis, reported by Moulton and Shaw in 1976, relied
on SN2 halide displacement from 1,3-C6H4(CH2Br)2 by tBu2PH followed by HBr
elimination [23]. Together with direct substitution by R2P (R ¼ Me, Ph) [24, 25],
with very few exceptions all dibenzylic phosphine pincer ligands with R ¼ tBu, Et
[26], iPr [27, 28], Cy [29, 30], and Ad [31] and other hydrocarbyl-substituted PCP
pincer ligands are prepared analogously. The preparation of unsymmetrical pincers
1,3-C6H4(CH2PR2)(CH2PR0 2) by sequential addition of secondary phosphines has
been reported [32]. Chiral PCP ligands with substituted CH(R) benzyl arms or mixed
PRR0 groups are known which similarly rely on SN2 substitution [33–38]. The
synthetic scope of this route is limited to sufficiently nucleophilic electron-rich PR2
groups, but any accessible 1,3-C6ExH4x(CH2Br)2 (E ¼ 6 H) precursors may be used
to prepare substituted aryl backbone pincer derivatives by this method (Scheme 1)
[39–51].
Most electron-withdrawing PCP systems have the general formula XPCP
(X ¼ electron-withdrawing group). To access dibenzylic pincer ligands with insuffi-
ciently nucleophilic R2PH or R2P precursors, however, alternative synthetic
approaches are required. In 2005, Milstein and van Koten introduced the use of the
diGrignard 1,3-C6H4(CH2MgCl)2 in the synthesis of the acceptor PCP ligands
52 D.M. Roddick
PNCNP pincer systems are thus far a relatively small subset in PCP coordination
chemistry and are prepared analogously to POCOP pincers using m-phenylenediamine
instead of a resorcinol derivative. Alkyl-substituted pincers RPNCNP (R ¼ iPr,
t
Bu, Ph) [63, 96] have been reported as well as ROPNCNP and R2NPNCNP systems
[63, 97, 98]. A single example of an asymmetrically substituted ligand, iPrPOCNP, has
been prepared by the reaction of m-aminophenol with one equivalent. n-BuLi followed
by the addition of two equivalents iPr2PCl [96].
56 D.M. Roddick
H Li
n −BuLi
N N R2PCI
PR2
H Li
N
Cl
PR2
N R2PH/base (R = Ar, iPr, tBu)
or R2P-
Cl
The formal substitution of a neutral pyridyl central group for an anionic aryl affords
the corresponding class of PENEP pincers (E ¼ CH2, NH, O) which may form
isoelectronic (RPENEP)MLn+ analogues to (RPECEP)MLn. An advantage of
pyridyl pincers is elimination of the aryl metallation step required in aryl pincer
terdentate coordination. The original synthesis of PhPNP, reported by Nelson in
1971 [99], involved the reaction of Ph2P-Na+ with 2,6-bis(chloromethyl)pyridine;
more recently, ArPNP ligands have been similarly using the appropriate Ar2PH with
t
BuOK+ (Scheme 6) [100]. In light of the advances achieved in PCP chemistry
using more electron-rich alkylphosphine pendant groups, the first alkylphosphine
R
PNP (R ¼ iPr, tBu) ligands were prepared more recently using the analogous
reaction of 2,6-bis(chloromethyl)pyridine with tBu2PH [101, 102] or iPr2PLi
[103], or from lutidine dilithiation followed by reaction with tBu2PCl [104]. The
neopentyl-substituted ligand NpPNP has also been prepared recently by the lutidine
dilithiation method [105]. MePNP has not been prepared synthetically, but is widely
used in metal complex calculations. As has been noted previously, the great
majority of current coordination chemistry research has focused almost exclusively
on the tert-butyl pincer tBuPNP.
Recognizing the susceptibility of PNP ligand systems to benzylic CH2 proton
loss to form dearomatized pincer complexes [106–108], and the enhanced reactivity
of POCOP relative to PCP iridium pincer complexes toward hydrocarbon dehydro-
genation [73], RPONOP (R ¼ iPr, tBu) pincer ligands have been prepared recently
for study [109–111]. Reaction of 2,6-dihydroxypyridine hydrochloride with two
equivalents of the appropriate dialkylphosphoryl chloride in the presence of base
directly affords PONOP ligands in moderate yield (Eq. 5). This synthesis is
analogous to POCOP syntheses and should readily generalize to any RPONOP
ligands where R2PCl precursors are available.
Tuning of PCP Pincer Ligand Electronic and Steric Properties 57
Since Tolman’s introduction of the simple cone angle model for assessing phosphine
sterics [114], a number of subsequent steric models have appeared [115–119]. Except
for a qualitative expectation of phosphine pincer sterics based on relative PR2
correlations to R3P steric size, the enveloping nature of pincer coordination imposes
a special case of steric influence. The “horseshoe” of ligand meridional coordination
blocks more than 180 of the equatorial volume about a metal, restricting approach to
the metal center trans to the M–C(aryl) bond axis, while PR2 steric bulk primarily
controls access to the metal center cis to the M–C(aryl) bond axis, above and below
the central aryl backbone plane (Fig. 1). Substitution of the central aryl backbone may
block access to the metal center to a lesser extent. The pronounced asymmetrical
steric influence of pincer ligands is similar in some respects to that of NHC ligands,
which have been analyzed using the percent buried volume approach (%Vbur),
a measure of the proportion of the first coordination sphere volume blocked by the
ligand in question [120, 121]. In Table 1 we summarize %Vbur data for selected
phosphine pincer systems. As noted previously, %Vbur values are sensitive to the
nature of the metal and remaining coordination environment LnM [121], but there is a
substantial body of structural data for (pincer)PdX (X ¼ Cl, Br, I) and other
4-coordinate 4d metal systems to allow many direct comparisons. Several trends
are apparent: (1) %Vbur values for the different pincer frameworks with the same
58 D.M. Roddick
tBu Ph
P P
tBu
Ph
(continued)
59
Table 1 (continued)
60
P P
POCOP ligands
Ir(CO) 4 69.3 0.6 157.6 [139]
tBu O O tBu Ir(PPh3) 4 65.1 1.3 155.3 [140]
P P
Tuning of PCP Pincer Ligand Electronic and Steric Properties
tBu tBu
(continued)
61
Table 1 (continued)
62
MeO OMe
Tuning of PCP Pincer Ligand Electronic and Steric Properties
tBu tBu
(continued)
63
Table 1 (continued)
64
PCNCP ligands
PdX 4 67.0 11.5, 7.7 169.4 [144]
Cy N Cy RuCl2(CC(TMS)Ph) 4 58.8 13.7 162.1 [145]
P P
Cy Cy
ReCl3 6 58.0 12.2 162.0 [144]
D.M. Roddick
Ir(C2H4)+ 4 72.8 9.9 164.3 [105]
Np N Np
P P
Np Np
Ph Ph
PNCNP ligands
PdCl 4 61.1 3.5 163.5 [63]
HN NH
Ph Ph
P P
Ph Ph
P P
iPr iPr
(continued)
65
Table 1 (continued)
66
PONOP ligands
Ir(Ph) 4 69.3 0.8 160.1 [109]
tBu O N O t Bu Ru(CO)H2 6 66.5 1.2 159.8 [111]
P P
tBu tBu
P P
i Pr iPr
PNNNP ligands
PdCl+ 4 60.9 1.3 166.4 [147]
HN N NH Mo(CO)3 6 55.2 1.4 155.0 [112]
Ph Ph
P P
Ph Ph
D.M. Roddick
Mo(CO)3 6 57.5 2.9 155.6 [148]
HN N NH iPr
iPr
P P
iPr iPr
Fig. 2 Effect of “pulled back” and “enfolded” geometries on trans void space
pendant phosphine groups, the factors which control the trans ligand void space are
more complex. In addition to phosphine group steric influence, the trans pocket is
dependent on the degree of pincer “pull-back,” which is controlled by both metal
bonding radii and subtending pincer arm metrics (Fig. 2). For a given pincer ligand
smaller metals with shorter M–C(aryl) and M–P bond lengths are enfolded more, as
illustrated by the significantly greater %Vbur value for (CyPCP)NiBr (75.0) com-
pared to (CyPCP)PdCl (66.2) [30, 130]. The smaller C(aryl)–O and O–P bond
lengths inherent in POCOP systems result in pincer pull-back and afford greater
steric access to the metal center. The more open trans void space of (tBuPOCOP)Ir
relative to (tBuPCP)Ir has recently been quantified by comparing the contact
distances between opposing tBu2P groups in DFT-optimized geometries (4.14 Å
versus 2.92 Å) [1]. This difference in steric access to the 3-coordinate catalyst
intermediate correlates with the increased alkane dehydrogenation activity of
iridium POCOP catalysts relative to PCP analogues.
bond lengths in POCOP pincers systems.1 Thus, the pendant PR2 groups for
POCOP systems have significantly smaller chelate bite angles and form essentially
planar 5-member chelate rings.
P–M–P angles subtended by pincer ligands are restricted by the metrics of the
P–E–Ar–E–P framework (E ¼ CH2, NH, O) to values less than 180 and readily
reflect steric influences about the metal coordination environment. For all
4-coordinate systems, a survey of the Cambridge Crystallographic Database gives
an average of 163 (range 152–173 ); for the subset of PCP pincers, the average is
higher (164.6 ) than for POCOP systems (160.6 ). For 6-coordinate systems the
overall P–M–P angle is 159.9 . The smaller average angle for POCOP systems is
consistent with the smaller covalent radius of oxygen. Two clear trends are evident:
(1) The smallest P–M–P angles are generally associated with a sterically demanding
ligand such as PPh3 trans to the pincer central aryl group. (2) In pincer systems where
steric demand is undifferentiated above and below the planes (i.e., in 4-coordinate
compounds and 6-coordinate compounds with trans ligands of comparable size),
decreases in P–M–P angles are due to bending toward the pincer aryl unit. In less
symmetrical complexes (such as 5-coordinate pincer complexes, discussed later), the
overall P–M–P angle is usually a combination of bending both parallel and perpendic-
ular to the C(Ar)–M bond axis. (3) The largest P–M–P pincer angles are associated
with smaller transition metals such as nickel in (C4H2Ph2PNP)NiBr+ Ni(H) (176.4 ),
where the N(Ar)-Ni bond length is 1.91 Å and the PNP ring can more effectively
enfold the metal center; for comparison, typical C(Ar)–M and N(Ar)–M bond
distances for 4d and 5d metals are ~0.1 Å longer.
An examination of PCP ligand C2 twist and P–M–P angles in Table 1 reveals a
rough inverse correlation between high C2 twist and small P–M–P angles: most
reported structures with C2 twists greater than 15 have P–M–P values below 160 .
For a given PCP pincer ligand system, these higher distortions accompany a
1
Pincer metrical parameters are obtained from the Cambridge Crystallographic Database, CSD
version 5.32, using data up till May 2011.
70 D.M. Roddick
The pincer complexes tabulated in Table 1 are, with one exception, restricted to
square planar and octahedral coordination complexes in order to simplify ligand
steric comparisons. However, a large number of 5-coordinate pincer systems are
known with coordination geometries that vary between the classical extremes of
trigonal pyramidal and square pyramidal ligand environments. Most structures can
be classified as one of four geometries, defined by angles a, b, g (Fig. 4). Many d6
metal complexes (Ru(II), Os(II), Rh(III), Ir(III)) adopt a relatively undistorted
square pyramidal geometry where a ~ 180 , g ~ 90 , and b ~ 160 (a typical
“unstrained” pincer P–M–P angle, rather than 180 ; see earlier discussion). Ru(II)
examples with little distortion include (tBuPCP)Ru(CO)2+ and (tBuPCP)Ru(H)(CO)
[61, 126]. For Rh(III) and Ir(III), there are many examples with a ~ 180 : (tBuPCP)
Rh(NO)(CO)+ and (tBuPNP)Rh(NO)(MeCN)2+ [149], (tBuPNP)Rh(NO)(Cl)+ [150],
(tBuPNP)Rh(Me)(Y)+ (Y ¼ I, CN) [151], (tBuPOCOP)Rh(X)(Y) (X ¼ H, Me,
CH2Ph; Y ¼ Cl or BF4) [152], (RPCP)Ir(H)(Cl) (R ¼ tBu, Ad) [31], (tBuPOCOP)
Ir(H)(Y) (Y ¼ NHC5F5, NHC(O)C6F5) [153], and (tBuPNP)Ir(H)(Ar)+ [154, 155].
A common feature of these structures is an apical X ligand with small steric demand
(H, Me, NO, CO), though undistorted complexes with flat or linear apical ligands
which fit well within the cleft above the pincer plane are known: (tBuPCP)Ir(X)(Y)
(X ¼ Ph, alkenyl, alkynyl; Y ¼ halide) [127, 156]. The complexes (tBuPCP)M
(CO)(Cl) (M ¼ Fe (a ¼ 164.3 ), Os (a ¼ 161.1 )) with apical CO ligands are
significantly distorted and are an exception to this trend [61, 157].
A series of PCP complexes (RPCP)M(PPh3)Cl (M ¼ Ru, Os; R ¼ Ph, iPr, Cy,
C6F5) with an apical PPh3 ligand have been reported with a reduced a value [33, 70,
158–160]. The P–M–P (b) values are less than those found in unstrained pincer
systems (151–159 ) and reflect a distortion of the pendant PR2 arms away from the
apical PPh3 ligand. a values do not simply correlate with R steric influence: R ¼ Ph
(153.4) > Cy(151.4) > iPr(146.6), but appear to track the ability of R groups to
flatten away from the Ph3P phenyl rings and influence the steric pocket about
the Y ligand (chloride). The least distorted structural example from this series is
(tBu,PhPCP)Ru(PPh3)Cl (a ¼ 169.4) [33], where the PPh3 ligand meshes well with
the pincer Ph and tBu groups and the PPh3 rings are staggered with respect to the
Ru–Cl bond. The most distorted example from this series, (C6F5PCP)Ru(PPh3)Cl,
(a ¼ 96.5 ) was reported by van Koten [159]. In this complex the pincer aryl
binding site assumes the apical position of a square pyramidal coordination and
C6F5 rings are engaged in p-stacking with the PPh3 rings. The Cl ligand is bent
drastically away to avoid steric interaction with the C6F5 ortho fluorines, but it is not
Tuning of PCP Pincer Ligand Electronic and Steric Properties 71
clear whether this unique coordination geometry is solely due to steric factors or the
electronic influence of the strongly p-accepting C6F5PCP ligand.
A series of 5-coordinate iron d6 PNP pincer complexes (RPNP)FeCl2 have been
structurally characterized which are significantly distorted from a square pyramidal
geometry (160 > a > 145 ; 149 > b > 140 ) [102, 113, 161, 162]. In these
systems the primary distortion is an elevation of the iron center above the pincer
backbone plane by 0.29–0.59 Å in order to accommodate unusually long N–Fe and
P–Fe bond distances to the high-spin iron center [102]. Cobalt(II) d7 5-coordinate
(ArPNP)CoCl2 complexes have also been reported [100]. The structures of these
compounds are best described as distorted trigonal bipyramidal, with axial PR2
pincer groups (b ¼ 155 ) and equatorial Cls (Ar ¼ o-tol: a ¼ 130.4 , g ¼ 111.9 ;
Ar ¼ Mes: a ¼ g ¼ 120.6 ). A very large pincer C2 twist of 27 is present in these
compounds and is probably induced by very long (2.62 Å) Co–P bonds to the high-
spin cobalt center.
5-Coordinate d8 pincer systems are much rarer. There are several examples of
zerovalent group 8 systems: (RPNP)Fe(CO)2 (R ¼ tBu, iPr) [102, 163] and
(tBuPONOP)Ru(CO)2 [111]. While (tBuPNP)Fe(CO)2 exhibits a Da, b square pyrami-
dal distortion (a ¼ 152.5, b ¼ 152.9 ), (iPrPONOP)Ru(CO)2 is more accurately
described by a Da, g TBP distortion (a ¼ 136.6, g ¼ 111.5 ). In contrast, (iPrPNP)
Fe(CO)2 adopts a nearly ideal TBP geometry with axial phosphorus ligation (a ¼ g
¼ 120.0 , b ¼ 166.0 ). Thus, relatively modest changes in pincer ligand sterics can
favor either SP or TBP geometries and the energetic difference is probably not large.
In 2005, Milstein reported the first examples of d8 M(I) 5-coordinate pincer
complexes, (pyrPCP)Rh(PR3)(CO) (R ¼ Ph, Et, pyr), formed from the reaction of
(pyrPCP)Rh(PR3) with CO [132]. Crystallographic data for (pyrPCP)Rh(PEt3)(CO)
72 D.M. Roddick
confirmed a relatively undistorted Db rather than a Da, g TBP geometry, with axial
CO and equatorial P(pyr)2 pincer and PEt3 groups (a ¼ 178.9, b ¼ 128.3 ,
g ¼ 87.9 ). More recently, an example of a d8 Co(I) pincer complex, (PhPOCOP)
Co(PMe3)2, has been reported [164]. As was the case for (pyrPCP)Rh(PR3)(CO),
(PhPOCOP)Co(PMe3)2 adopts a Db distortion which places the pincer phosphorus
groups and one PMe3 in the TBP equatorial plane (a ¼ 172.0, b ¼ 131.5 ).
Milstein has argued on the basis of DFT calculations that coordination of a fifth
ligand to square planar (pyrPCP)Rh(PR3) systems is favored by stabilization of a bent
“see-saw” geometry by the electron-withdrawing pyrrolyl phosphine substituents,
which lower the energy of the frontier d orbitals [132]. The 5-coordinate dicarbonyl
complex (pyrPCP)Rh(CO)2 was predicted to be marginally stable (DH(CO dissociation)
~3 kcal mol1) but was not prepared. As part of our research program exploring the
chemistry of perfluoroylalkylated phosphine complexes, we recently reported the
synthesis of Ir(I) pincer complexes incorporating the strong acceptor ligand CF3PCP
[137]. In agreement with Milstein’s prediction, a series of stable 5-coordinate Ir(I)
complexes (CF3PCP)Ir(L)(L0 ) (L ¼ L0 ¼ CO, MeP(C2F5)2; L ¼ C2H4, L0 ¼ PhCN;
L, L0 ¼ cod, nbd, (C2F5)2PCH2CH2P(C2F5)2) were isolated and structurally
characterized. All nonchelating systems were found to adopt TBP geometries with a
Db distortion and equatorial pincer P(CF3)2 groups ((CF3PCP)Ir(CO)2: a ¼ 171.6,
b ¼ 130.3 ; (CF3PCP)Ir(MeP(C2F5)2)2: a ¼ 173.6, b ¼ 124.2 ; (CF3PCP)Ir(C2H4)
(PhCN): a ¼ 177.9, b ¼ 123.8 ).
In general, unequal steric influence above and below the nominal pincer chelate
plane in 5-coordinate systems leads to a decrease in P–M–P angles. Besides the d8
and d6 systems discussed above, several examples of pincer complexes with small
P–M–P angles which can be more accurately described as “cisoidal” have been
reported. The most exceptional examples are Jia’s osmium 3-legged (Z5-C5HxR5x)
Os(PhPCP) and 4-legged (Z5-C5HxR5x)Os(PhPCP)(X) piano-stool compounds with
P–Os–P angles as small as 107–108 [165]. As part of our studies of (CF3PCP)Ir(L)
(L ¼ CO, MeP(C2F5)2) chemistry, we have reported the reaction of (CF3PCP)Ir
(MeP(C2F5)2) with H2 to form what can be best classified as a 6-coordinate complex
with a facial pincer, fac,cis-(CF3PCP)Ir(MeP(C2F5)2)(H)2 with a P–Ir–P angle of
118 (Eq. 7) [137]. VT NMR confirmed that the reaction of (CF3PCP)Ir(CO) with
H2 similarly proceeds via the intermediacy of fac,cis-(CF3PCP)Ir(CO)(H)2.
Fig. 6 Calculated (RPCP)Ir(CO) P–Ir–P bending energetics. DFT tpssh meta-GGA functional
(Gaussian 09 Rev A.02) using Dunning cc-pVDZ basis sets with augmented diffuse P, F, and N.
Figgen pseudopotentials and a correlation-consistent diffuse basis set for iridium were used [168]
Fig. 8 Calculated (RPCP)Ir(NH3) P–Ir–P bending energetics. DFT calculations carried out as
described for Fig. 5
for R ¼ F and CF3 pincer distortion is very small, <0.5 kcal mol1), the same basic
trend is observed. At the maximum distortion angle calculated, 40 , the difference in
energy between the strongest pincer acceptor, R ¼ F, and the donor R ¼ Me is only
6.3 kcal mol1. As noted by Milstein, the strongest acceptor pincers have the least
energetic cost for bending into a “see-saw” configuration. Methyl fluorination has
virtually no net effect on bending energetics: at D(P–Ir–P) ¼ 40 , the difference in
DE for both Ir–CO and Ir–NH3 derivatives is less than 1 kcal mol1. The similarity
between R ¼ CF3 and CH3 pincer systems is likely due to a compensating steric
destabilization for the larger CF3 groups. At 40 the larger (iPrPCP)Ir(CO) complex
is destabilized relative to (MePCP)Ir(CO) by only ~3.5 kcal mol1.
It is clear from Figs. 6 and 8 that the dominant factor in bending energetics is the
steric influence of the phosphine substituents. tbutyl pincer systems pay the highest
price: while relatively flat R ¼ iPr and pyr substituents adopt rotamer conformations
that minimize PR2 axial–axial repulsions, the rigid nature of aryl-bridged terdentate
ligands enforces a highly unfavorable tBu–tBu interaction. The highest destabiliza-
tion is found for the POCOP system (~10 kcal mol1 relative to tBuPCP), which has
shorter pendant arm bond lengths and the least conformational flexibility. The
chemical and structural consequences for 5- and 6-coordinate complexes with
non-meridional pincer ancillary ligands (Db distortions) are very significant. Taking
Me
PCP as a baseline, we can estimate the steric cost for the most commonly used
pincer types, tBuPECEP and tBuPENEP as being 12 < DE < 20 kcal mol1 for
76 D.M. Roddick
non-meridional pincers with 130 > b > 120 and E ¼ CH2, to as much as 18 <
DE < 30 kcal mol1 for POCOP and PONOP systems. PNCNP and PNNNP
systems should have an intermediate pincer distortion behavior. In our discussion
of non-meridional reaction intermediates (see earlier), we noted the surprising
failure of (tBuPCP)Ir(CO) to react with H2 [166]. Assuming b ¼ 130 for an initial
H2 adduct (tBuPCP)Ir(CO)(H2), we can estimate a steric destabilization of
~10 kcal mol1 relative to (iPrPCP)Ir(CO)(H2), which may be sufficient to account
for the observed substituent effect. This t-Butyl substituent steric effect is
illustrated very nicely by Krogh-Jespersen and Goldman’s combined theoretical
and experimental study of alkane dehydrogenation by (R4PCP)IrH4 (R ¼ tBu or
Me) systems [32]. Substitution of only one tBu group by Me results in a calculated
10 kcal mol1 decrease in the b-H elimination transition state and a corresponding
increase in catalytic activity. Further methyl substitutions result in less dramatic
effects and complex oligomerization becomes favored. These observations are
consistent with the idea that removing even a single tBu group greatly facilitates
non-meridional pincer bending.
Despite the variety of ligand variation in phosphine and arene ring substituents as
well as pincer linkages (CH(R), NH, O), relatively little in the way of direct
systematic experimental comparisons of pincer electronic influence has been
reported. Most available comparative n(CO) data concern isostructural RPCP and
R
POCOP complexes and variations in phosphine R groups. Very little information
exists for analogous PNCNP carbonyl compounds. Table 2 summarizes n(CO) data
for isostructural classes of pincer carbonyl complexes where a suitable range of
systematic data has been reported. Only a single direct comparison of PNCNP
versus POCOP has been reported, (pipPNCNP)Pd(CO)+ (n(CO) ¼ 2,106 cm1) and
(pipPOCOP)Pd(CO)+ (n(CO) ¼ 2,133 cm1), which clearly shows the expected
greater electron donating influence of RPNCNP relative to RPOCOP [93]. Some
direct RPOCOP comparisons to corresponding RPCP carbonyl compounds are
available: (RPCP)M(CO) and (RPOCOP)M(CO) (M ¼ Rh, Ir; R ¼ tBu, iPr)
systems have Dn(CO)’s of 21–26 cm1. This increase in n(CO) going from RPCP
to RPOCOP is similar to the 27 cm1 difference between pipPNCNP and pipPOCOP
and suggests that the baseline donating abilities of RPCP and RPNCNP ligands are
comparable. This similarity most likely reflects a balancing of electron-
withdrawing NH pincer arms on phosphine donor ability and NH p-donation into
the central aryl backbone.
Trends in phosphine substituent influence on n(CO) follow the expected order of R
donor ability, as judged by Hammett sm parameters: [174, 175] Ad(0.12) > tBu
Tuning of PCP Pincer Ligand Electronic and Steric Properties 77
63
Pt(CO)+ systems
(tBuPCP)Pt(CO)+ 2,074 [171]
(iPrPCP)Pt(CO)+ 2,080 [171]
(CF3PCP)Pt(CO)+ 2,143 [55]
69
Ir(CO) systems
(AdPCP)Ir(CO) 1,916 [31]
(Me2N-tBuPCP)Ir(CO) 1,918 [42]
(MeO-tBuPCP)Ir(CO) 1,923 [42]
(H-tBuPCP)Ir(CO) 1,925 [42]
(MeO2C-tBuPCP)Ir(CO) 1,931 [42]
(tBu2PO-tBuPOCOP)Ir(CO) 1,934 [42]
(MeO-tBuPOCOP)Ir(CO) 1,947 [172]
(Me-tBuPOCOP)Ir(CO) 1,947 [172]
(H-tBuPOCOP)Ir(CO) 1,949 [172]
(F-tBuPOCOP)Ir(CO) 1,953 [172]
(C6F5-tBuPOCOP)Ir(CO) 1,955 [172]
(ArF-tBuPOCOP)Ir(CO)a 1,955 [172]
(tBuPNP)Ir(CO)+ 1,962 [173]
(CF3PCP)Ir(CO) 2,018 [137]
102
ArF ¼ 3,5-(CF3)2C6H3
a
(0.10) > Me(0.07), Cy(0.05), iPr(0.04) > Ph(0.06) > PhO(0.25) > CF3(0.43).
Brookhart has reported a range of (R-tBuPOCOP)Ir(CO) derivatives which provide
a measure of the para ring substituent effect on pincer electronics, ranging from
electron-donating R ¼ MeO (n(CO) ¼ 1,947 cm1) to electron-withdrawing R ¼ C6F5
(n(CO) ¼ 1,955 cm1) [172]. The small Dn(CO) of 8 cm1 range indicates that para
effects are quite minor. An identical Dn(CO) ¼ 8 cm1 for R ¼ MeO to C6F5 is seen for
(R-tBuPCP)Ir(CO) systems [42].
Goldman and Krogh-Jespersen have carried out a DFT analysis of the contrasting
effects of O ! C(aryl) p-donation for (R-tBuPCP)Ir and (R-tBuPOCOP)Ir (R ¼ H or
MeO) and have concluded that the induced net charge effects on iridium for PCP and
POCOP pincer frameworks are actually quite comparable [176]. The ~20 cm1
increase in n(CO) for POCOP carbonyl systems relative to PCP analogues was
78 D.M. Roddick
N N P N P N P N
Me2 iPr Ph2 (CF3)2
2
(PhPCP)Ru(tpy)+ (+0.167 V), and Ru(tpy)2+ (+1.32 V) give the ligand donor
strength ordering MeNCN > iPrPCP > PhPCP tpy (Fig. 9) [129]. While the
111 mV difference between the PCP systems can be readily attributed to the more
electron-releasing nature of iPr relative to Ph, the stronger donating ability of
Me
NCN is not as readily explained. The presumed greater affinity of Ru3+ for harder
NCN Lewis base provides a tentative qualitative rationale.
We have recently prepared the analogous ruthenium terpyridine complex
(CF3PCP)Ru(tpy)+ and examined its electrochemistry (Adams JJ, Roddick DM,
unpublished results). In acetonitrile (0.1 M TBAP) a fully reversible Ru(II)/Ru
(III) oxidation couple is observed at a remarkably high potential of +0.852 V. The
increase of 0.7–0.8 V in oxidation potential relative to ruthenium supported by
iPr
PCP and PhPCP pincer ligands (Fig. 9) is slightly less than the effect on oxidation
potentials previously reported by us for the replacement of aryl or alkyl groups with
perfluoroethyl groups in chelating phosphine systems: DEox ¼ +1.3 V (CpMn
(dfepe)(CO) (dfepe ¼ (C2F5)2PCH2CH2P(C2F5)2) versus CpMn(PPh3)2(CO))
[178], DEox ¼ +1.3 V (Cp*Ru(dfepe)Cl versus Cp*Ru(depe)Cl) [179], and
+0.9 V ((Z6-arene)Mo(dfepe)(CO) versus (Z6-arene)Mo(dppe)(CO)) [180]. The
very large electron-withdrawing inductive effect of perfluoroalkyl groups on phos-
phine ligands is broadly established by electrochemical data across a range of metal
systems.
Zargarian has recently presented E1/2(Ni(II)/Ni(III)) data for analogous PCP and
POCOP complexes, as well as a related hydrocarbyl-bridged pincer compound:
[(tBu2PCH2CH2)CH]NiBr (0.01 V), (iPrPCP)NiBr (+0.34 V), (iPrPOCOP)NiBr
(+0.64 V), and (3,5-Cl2-iPrPOCOP)NiBr (+0.75 V) (Fig. 10) [181, 182]. The
increase of 330 mV in oxidation potential between the hydrocarbyl- and aryl-
bridged pincer complexes is consistent with the greater electron-donating ability
of the C(sp3) relative to C(sp2). The 300 mV difference between corresponding PCP
and POCOP complexes is the only literature example thus far of the greater
electron-withdrawing effect of the POCOP ligand. Interestingly, the addition of
two meta Cl substituents to (iPrPOCOP)NiBr results in only a 110 mV increase in
oxidation potential, significantly less than the 280 mV reduction in oxidation
potential induced by the presence of a single MeO para group in (MeO-tBuPCP)Ir
(H)Cl (see above).
Van Koten’s 2005 comparison of (RPCP)Ru(Ph3P)Cl (R ¼ C6H5, C6F5)
complexes confirmed both structural and electronic effects imparted by aryl
80 D.M. Roddick
dissociation value for (CF3PCP)Ir(CO)2, 13.2 kcal mol1, is consistent with the
9.7 kcal mol1 experimental value obtained from dynamic NMR data. DGdiss(Ir–CO)
for (C6F5PCP)Ir(CO)2 is slightly less than predicted and probably reflects some steric
destabilization. Once again, the general picture is that pincer electronic effects are
significant, but any process which involves non-meridional pincer bending is
dominated by steric destabilization in tBu-substituted pincer systems.
5 Summary
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Tuning of PCP Pincer Ligand Electronic and Steric Properties 87
Abstract Pincer ligands of the form ECE that incorporate N-heterocyclic lateral
units, E, are terdentate analogues of NC-cyclometallating ligands such as
2-phenylpyridine. They are able to form a variety of highly luminescent complexes
with platinum(II) and iridium(III). They can also be thought of as cyclometallating
analogues of the NNN-coordinating ligand terpyridine. The introduction of the
carbon atom can impart significant changes on the nature and energy of the
electronic excited states, as is evident for complexes of ruthenium(II), where a
shift in the absorption to low energy in the metallated systems has sparked interest
in applications for dye-sensitised solar cells. Investigations in these areas over the
past decade are reviewed. We also consider related complexes in which the lateral
coordinating units are aliphatic N donors, phosphines, or sulphur ligands. The lack
of good p-accepting units in such compounds tends to lead to weaker ligand fields
and hence to low-energy metal-centred states. These states dictate much of the
excited-state chemistry and compromise the efficiency of luminescence at room
temperature.
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
2 Complexes of SCS Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3 Complexes of PCP Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
1 Introduction
a b c
N N N N N
M M M
a b
Energy Energy
d-d d-d
d-p*
excited state or p-p*
DE
Fig. 2 (a) Metal-centred d–d excited states involve population of strongly antibonding orbitals,
such that the potential energy surface of the excited state is severely displaced relative to that of the
ground state. (b) At a given temperature T, the d–d state can provide a thermally activated pathway
for other, lower-lying excited states if DE is comparable to kT. Thick arrows represent absorption
of light; thin ones indicate vibrational relaxation and non-radiative decay [13]
Cl
1 M = Pd 2 M = Pt
Fig. 3 The synthesis of SCS-coordinated Pt(II) and Pd(II) complexes incorporating phosphine
sulphide ligands [14]
N N
N N H S S
Pt
S Pt S CuI Et3N
Cl
3 4
Fig. 5 Electroluminescence spectra of OLEDs prepared using 3 and 4 as emitters in the multilayer
device structure shown in the inset. BPhen bathophenanthroline, PVK poly(9-vinylcarbazole),
BuPBD 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxa-diazole, PEDOT-PSS poly
[3,4-(ethylenedioxy)thiophene]-poly(styrenesulfonic acid)} (reprinted with permission from [15]
# 2004 Elsevier)
Related secondary thioamide pincer ligands form similar complexes but those of
N-arylthioamides offer additional scope due to the possibility of subjecting them to
oxidative cyclisation reactions. Thus, proligand 5 can be cyclised to give 6 upon
treatment with K3[Fe(CN)6] (Fig. 6) [17]. Both complexes react with K2PtCl4 to
form complexes in which the ligand is bound in a terdentate pincer fashion (7 and
8 respectively) but, whereas the ligand is SCS-coordinating in 7, it binds as an
NCN-coordinating ligand in 8, owing to the very poor ligating properties of the
sulphur atoms in benzothiazoles.
Both complexes emit in the solid state at room temperature and in a frozen glass
at 77 K, but only the NCN-coordinated complex 8 is luminescent in fluid solution at
room temperature. Though the authors did not comment on the likely origin of this
difference, we speculate that the weaker ligand field strength offered by SCS-
coordinating ligands compared to aromatic NCN ligands may lead to metal-centred
excited states being thermally accessible at room temperature, thus introducing an
additional deactivation pathway, as mentioned in the Introduction. It is also likely
that the SCS complex will be less rigid, favouring intramolecular electronic-to-
vibrational energy transfer and subsequent energy loss to the solvent. Indeed, such
characteristics would apply equally to complexes 2–4 discussed above.
The emission spectra of 7 and 8 at 77 K are shown in Fig. 7. The SCS complex 7
displays a broad structureless spectrum in the red region, which is assigned to a
3
MLCT state. In contrast, the spectrum of the NCN-coordinated complex appears at
Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and. . . 95
K2PtCl4
H H H H
N N N N
Ph Ph Ph Ph
S S S S
Pt
5
Cl
K3Fe(CN)6 SCS-coordination
7
K2PtCl4
S S S S
N N N N
Pt
6 Cl
NCN-coordination
8
Fig. 6 SCS and NCN coordinated pincer Pt(II) complexes derived from the thioamide
proligand 5 [17]
higher energy and reveals well-resolved vibrational structure, a feature more typical
of excited states of predominantly ligand-centred (3p–p*) character. Indeed the
profile of the spectrum is similar to that of the Pt(II) complex of 1,3-
dipyridylbenzene (see Sect. 5.3.1), where a ligand-centred assignment is generally
accepted, but with an emission energy somewhat lower, consistent with the
expected decrease in excited-state energy on going from pyridine to benzothiazole
units. In the solid state at room temperature, the emission is red-shifted in both cases
compared to that in solution, suggesting the formation of aggregates or excimer-like
species, an observation in line with the rather short interplanar distances of 3.56 and
3.40 Å in the crystal structures of 7 and 8, respectively.
More recent work from the same group has focused on the reactivity of the
thioamide N–H in such secondary thioamide complexes: it can be deprotonated by
strong bases and can also act as a hydrogen bond donor, with the potential to lead to
modulation of the ground-state absorption and excited-state emission properties [18].
Investigations were carried out on the dibenzylaminothiocarbonyl complex 9 (Fig. 8).
In contrast to its anilinothiocarbonyl analogue 7, complex 9 is luminescent in solution
at room temperature (Flum ¼ 0.06 in THF). Upon addition of increasing amounts of a
strong base such as DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), the absorption spec-
trum changes, as shown in Fig. 9a, with two well-defined isosbestic points, until the
point at which two equivalents of base have been added relative to 9. The changes in
absorption are accompanied by a decrease in the emission intensity (Fig. 9b). The
original spectra are restored upon addition of methanesulfonic acid, and hence the
effect is interpreted in terms of the reversible equilibria shown in Fig. 8. The excited-
state pKa of 9 was estimated to be 17.7.
In contrast to the effect of base, the addition of tetra-n-butylammonium chloride
to a solution of 9 leads to a blue-shift in the lowest-energy absorption band and of
the emission (Fig. 9c, d). The emission intensity is enhanced, and the lifetime is
96 G.R. Freeman and J.A.G. Williams
Fig. 7 Emission spectra of the Pt(SCS) complex 7 and Pt(NCN) complex 8 at 77 K in a frozen
glass of CH2Cl2/THF (3:2 v/v) (reprinted with permission from [17] # 2006 American Chemical
Society)
– 2–
H H H
Ph N N Ph Ph N N Ph Ph N N Ph
S S – H+ S S – H+ S S
Pt Pt Pt
Cl + H+ Cl + H+ Cl
9 9–H+ 9–2H+
Fig. 8 Pt(II) SCS pincer complex 9 and the reversible double-deprotonation reaction it undergoes
upon treatment with strong base
Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and. . . 97
a 1.0
c
0.0 equiv of DBU 1.0
Abs. at 450 nm
0.4 0.2 600
0.3 0.4 400
0.6 200
Absorbance
Absorbance
Relative Intensity
200
0.8 0.8
1.0 100
1.2 1.5 50
0.6 1.4
1.6
20
10
1.8
1.0 632 0 equiv of TBACI
0.4 2.0
0.2 0.5
0.0 0.0
550 600 650 700 750 800 500 550 600 650 700 750 800
Wavelength / nm Wavelength / nm
Fig. 9 Left: Changes in the (a) absorption (inset: absorbance change at 450 nm) and (b) emission
spectra of 9 (5 105 M in THF at room temperature) upon addition of DBU. Right: Changes in
the absorption (c) and emission (d) spectra of 9, under the same conditions, upon addition of
[Bu4N]+Cl (reprinted with permission from [18] # 2009 American Chemical Society)
increased. These effects have been interpreted in terms of hydrogen bonding of the
N–H of the thioamide group to the added chloride ions. It is suggested that this
interaction may either inhibit the quenching of the 3MLCT state by the solvent or
help to rigidify the molecules in solution, making non-radiative decay pathways
less efficient. In line with this notion is the magnitude of the effect with other
anions, being in the order Cl > Br > BF4 > PF6, which mirrors their hydro-
gen bond acceptor ability. The lack of any changes in the absorption spectrum of a
related dimethylaminothiocarbonyl complex (a tertiary thioamide) upon addition of
either base or chloride ions also confirms the requirement for the N–H unit,
supporting the proposed hypotheses.
Finally in this section, we note that asymmetric SCS ligands incorporating one
thioamide and one phosphine sulphide unit have recently been reported, and the
palladium complex of one such ligand displays weak emission in the deep-red/NIR
region (lmax ¼ 740 nm) in the crystalline state at room temperature [19].
O
O2 O
HO
P P hn P P P P
Ph Pt Ph Ph Pt Ph Ph Pt Ph
Ph Ph Ph Ph Ph Ph
Cl Cl Cl
Pt(II)-endoperoxide
10 11 O2
OH–
O O O
O O HO O
Ph P P Ph Ph P P Ph P
Pt Pt Ph Pt P Ph
Ph Ph Ph Ph Ph Ph
Cl Cl Cl
12b 12a
to the Pt(II) ion through the two phosphorus atoms to give complex 10 (Fig. 10).
The corresponding compounds with bromide or iodide in place of chloride as the
co-ligand could be prepared from 10 by halide metathesis. The low-energy,
vibronically resolved 1p–p* bands typical of anthracene (in which they appear at
380 nm) are modestly red-shifted on going to DPA and shifted substantially further
in 10 (Fig. 11). Transitions of MLCT and LLCT character are also anticipated on
the basis of symmetry, but these are presumably masked by the ligand-centred
transitions. Complex 10 is strongly photoluminescent in deoxygenated
Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and. . . 99
dichloromethane solution at room temperature (lmax ¼ 474 nm, Flum ¼ 0.22). The
small Stokes shift of 900 cm1 relative to the lowest-energy absorption band has
been interpreted as indicative of emission from the p–p* state, although whether
this has singlet or triplet character is not clear from the report. No luminescence
lifetime is available, but the emission is modestly quenched by O2 (intensity in air-
equilibrated solution is 70 % of that of a degassed solution), suggesting that the
lifetime is likely to be at least tens of nanoseconds.
Upon irradiation of an air-saturated “wet chloroform” solution of 10, the com-
plex undergoes photo-oxidation to generate a deep-red Pt(II)–hydroxyanthrone
complex (11), which has been unequivocally identified by X-ray crystallography.
The consequent disruption of the conjugated system of the anthracene unit is
reflected in the bleaching of the p–p* transitions, but this is accompanied by the
appearance of much weaker bands centred at 538 and 706 nm. On the basis of the
known spectroscopy of anthrones [21], these bands are attributed to formally
forbidden 1n ! p* and 3n ! p* transitions, respectively. Complex 11 is weakly
emissive in the NIR region (lmax ¼ 732 nm, Flum ¼ 3 103 in CH2Cl2, Fig. 11).
The conversion of 10 to 11 is thought to proceed via the 9,10-endoperoxide, formed
by reaction with 1O2. The complex itself is likely to be able to sensitise dissolved
oxygen to the singlet state. The role of 1O2 is supported by the observation that the
rate of reaction is faster in CDCl3 than in CHCl3, consistent with the longer lifetime
of 1O2 in the former solvent (300 ms compared to 30 ms respectively).
Upon prolonged further irradiation in the presence of O2, 11 is oxidised to 12a
(identified in solution), which undergoes acid-catalysed ketalisation to generate 12b
(crystallographically characterised). The formation of these products from 11, and
their interconversion, is thought to proceed via a Pt(II)-anthraquinone intermediate.
The oxidation of 11 to 12a also proceeds in darkness, but at a much slower rate,
which is interpreted in terms of sensitisation of 1O2 (more oxidising than ground
state 3O2) by 11 in the presence of light.
Overall, the study shows that the platinum(II) ion has a profound influence on the
photo-oxidation of the anthracene unit. It contrasts with the behaviour of anthracene
itself which, following the formation of the endoperoxide, gives rise to a range of
photoproducts and thermal products.
A ruthenium(II) complex incorporating a PCP-binding ligand has been
investigated as a sensitiser of lanthanide(III) excited states [22]. The lanthanide
(III) ions suffer from low molar absorptivities (for the f–f excited states), and the
strategy of using d-block complexes as “antennae” is one which has been widely
explored over recent years [23]. The excited state of the sensitiser moiety should be
higher in energy than the lanthanide excited state, in order for efficient energy
transfer to occur. The ruthenium complex 13 (Fig. 12), related to the widely studied
complex [Ru(tpy)2]2+ and its cyclometallated analogues (see Sect. 5.1), shows no
detectable emission, even at 77 K, possibly owing to quenching by the anilino
nitrogen atom. However, upon binding of the pendant azacarboxylate to Gd3+ (13-
Gd), weak emission bands are observed at 560 and 650 nm, attributed to 3LC and
Ru-based 3MLCT states, respectively. Apparently, the binding of the lanthanide ion
attenuates the quenching effect of the amine. The 3LC excited state of the system is
100 G.R. Freeman and J.A.G. Williams
NaO2C
Ph N CO2Na Ph N
Ph Ph CO2– H
N N
P LnCl3.6H2O P CO2– O
3+ H
Ru N N Ru N N Ln
O H
P CO2Na P CO2–
N N H
Ph Ph CO2–
Ph N Ph N
CO2Na
13-Gd Ln3+ = Gd3+
13
13-Eu Ln3+ = Eu3+
R R
+ SO2
Fig. 13 NCN-coordinated Pt(II) complexes with saturated amine donors can bind SO2 reversibly
sufficiently high to be able to populate the 5D0 state of Eu3+ and, indeed, in the
corresponding Eu3+ complex (13-Eu), a weak band is observed, attributable to the
5
D0 ! 7F2 transition, together with the lower-energy 3MLCT state band. Energy
transfer from the Ru-based 1MLCT and from the 3LC states to the Eu3+ ion is
inferred. The origin of another sharp band at 545 nm in the Eu3+ complex is,
however, unclear.
X=
17 Cl
18 Br
N Br N N N 19 I
Pt
16 X 20 N
+ 2+
N N
N N
Pt
Pt N N Pt
N
N N
21 R = H 23
22 R = Ph
Fig. 14 A selection of NCN-coordinated pincer Pt(II) complexes prepared by Connick and co-
workers from proligand 16
the UV, displaying intense bands in the 250–300 nm region (e > 7,000 M1 cm1)
which have no counterparts in the uncomplexed proligand (Fig. 15a). These bands are
attributed to MLCT transitions; metal-centred d–d states would be expected at
higher energies and, being formally forbidden, would have smaller extinction
coefficients. The MLCT assignment is supported by the observed trend in energies:
20 > 17 > 18 > 19; i.e. the transition shifts to lower energy with increasing elec-
tron density on the metal centre. A weaker shoulder around 300 nm is visible for all
but the iodo complex, which is attributed to the formally spin-forbidden transition to
the corresponding 3MLCT state: the singlet-triplet splitting of around 2,500 cm1 is
of an order of magnitude typical for MLCT states of Pt(II) diimine complexes [32].
No luminescence could be detected from the complexes in solution at room
temperature but, at 77 K in a frozen glass, all four display orange to red emission,
with broad, Gaussian-shaped bands (Fig. 15b). The luminescence is attributed to
3
MC excited states, i.e. of dp(xy,xz,yz) ! ds*(x2y2) character. The order of
emission energies is 20 > 17 > 18 > 19, consistent with the positions of the
monodentate co-ligands in the spectrochemical series. The weak band around
370 nm observed in the excitation spectra (Fig. 15b), and whose position displays
the same trend in energy, is likely to be due to direct excitation to the 3MC state.
The large Stokes shifts and broadness of the emission bands are consistent with a
relaxed excited-state geometry that is very different from that of the ground state, as
expected for an excited state that involves population of an antibonding (i.e. dx2 y2 )
orbital.
Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and. . . 103
Fig. 15 (a) Room temperature absorption spectra of 17–20 in MeOH. (b) Normalised emission
spectra of 17–20 at 77 K in a glass of EtOH/MeOH (3:1 v/v) with corresponding excitation spectra
shown in the left panel (reprinted with permission from [29] # 2002 American Chemical Society)
The authors noted that the emission of the imine and chloro complexes, 20 and
17, appears at lower energies than that observed from Pt(NH3)2Cl2, despite the
generally accepted view that the phenyl anion should be a stronger field ligand than
imine or chloride. They note the importance of the orientation of the ring with
respect to the orbitals of the metal ion. In the NCN complexes, it is not optimised
for p-back-bonding with the dxy level, and therefore the dxy ! ds* energy gap is
low. On the other hand, the orientation of the phenyl ring favours relatively low-
energy Pt ! phenyl MLCT excited states. These occur at 270–285 nm for the
present set of complexes, compared to shorter wavelengths (<260 nm) for the
corresponding transitions in Pt(PEt3)2PhCl, where the phenyl rings are tilted rela-
tive to the coordination plane.
104 G.R. Freeman and J.A.G. Williams
Fig. 16 Emission spectra of 21–23 at 77 K in a glass of EtOH/MeOH (4:1 v/v) together with that
of 17 and of 4-phenylpyridine (dotted line) and 4,40 -bipyridine (dashed line) under the same
conditions for comparison (reprinted with permission from [30] # 2004 American Chemical
Society)
H O R=
R
a NMe2
1. t-BuOK, THF b OMe
+
OEt 2. H2O, NaCl c SiMe3
N N OEt d H
Pt P
O e I
Cl
N N f CN
Pt
27 g NO2
Cl
28a-g
0.3
Absorbance
0.2
0.1
0.0
270 320 370 420 470 520 570
Wavelength [nm]
Fig. 18 Absorption spectra of 28a–g in CH2Cl2, together with that of DANS for comparison
(reprinted with permission from [33] # 2007 Wiley-VCH)
lifetime of the order of 200 ps in CH2Cl2, suggestive of a singlet rather than triplet
origin, despite the presence of the heavy metal ion. One possible explanation is that
the rate of fluorescence is too fast—and the SOC effect of the platinum(II) in the
excited state is too small in such extended conjugated systems—for efficient ISC to
the triplet state to compete with fluorescence. However, the quantum yields of
fluorescence are much lower than those of organic stilbenes. Thus, it is quite
possible that ISC is highly competitive with fluorescence but that the triplet state,
once formed, does not lead to observable phosphorescence under ambient
conditions, due to efficient non-radiative decay pathways. Support for the latter
explanation comes from recent studies of the electroluminescence of an OLED
fabricated using a spin-coated layer of 28f as the emitting layer [34]. It was noted
that the EL spectrum of the device was dominated by an emission band around
470 nm, consistent with the behaviour of this complex in solution. However, an
additional longer wavelength band was also observed, at around 650 nm. This
observation prompted a study of the emission of 28f in the solid state. At low
temperatures, a new band appears at 660 nm, accompanied by the second compo-
nent of a vibrational progression visible at 730 nm. These bands are attributed to
phosphorescence from the triplet state, which is quenched by non-radiative decay
processes at ambient temperature. A similar situation has been observed in
cyclometallated platinum(II) complexes with phenylpyridine ligands incorporating
styryl substituents [36].
Finally, we note that the NLO properties of these complexes have been explored.
The incorporation of metal fragments into conjugated organic systems is one which
is opening up new possibilities in the field of NLO [37, 38]. The bzzz component of
the hyperpolarisability tensor (where z is the charge transfer axis) has been deter-
mined for 28a–g by hyper-Rayleigh scattering, from which the static quadratic
hyperpolarisability, b0, is calculated. The complexes show values of b0 (up to
211 1030 esu for R ¼ I) that are similar to or higher than those of purely
Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and. . . 107
organic stilbenes such as DANS (b0 ¼ 56 1030 esu), probably reflecting poten-
tial for polarisation along the C–Pt bond. There is, however, no clear-cut correlation
between the donor or acceptor properties of the R group and the magnitude of b0,
probably because of the dependence of the latter not only on the energy of the first
excited state, but also on the absorption coefficient, and possibly also on
contributions of other excited states.
1,3-Bis(20 -imidazolinyl)benzene ligands are under investigation as analogues of
the well-known chiral pincer ligands based on 1,3-bis(20 -oxazolinyl)benzene
(phebox) [39, 40]. Ligands of this type form chiral C2-symmetric complexes
upon NCN-cyclometallation with metal ions such as palladium(II) and platinum
(II). The luminescence properties of the complexes 29a–d have been investigated
by Hao et al. [41]. These complexes are all luminescent in solution at room
temperature. Although the quantum yields are quite low, 0.13–0.18 %, the
behaviour contrasts with that of related complexes discussed earlier in this section
with saturated nitrogen donors (e.g. 17–20), for which luminescence is only
observed at low temperature. The emission maxima in CH2Cl2 solution are around
575 nm in each case: the substituents have no significant effects. A further differ-
ence is that the complexes are yellow rather than colourless. These differences that
arise upon changing from amine- to imine-based ligands can be understood in terms
of two effects of the introduction of the C¼N bonds. Firstly, the p-acceptor nature
of the C¼N bond should serve to stabilise the 1,3MLCT states. Secondly, the ligand-
field strength of an imino-NCN ligand should be greater than for an amino-NCN
analogue, such that 1,3MC (d–d) states will be destabilised. Thus, one might
anticipate that the lowest energy excited states in 29a–d will be 3MLCT in
character, less subject to distortion compared to the MC states of 17–20, and thus
less prone to non-radiative deactivation. Indeed, one might regard these complexes
as being intermediate in nature between the fully saturated and the aromatic NCN
systems discussed in Sect. 5.3, where substantially higher quantum yields are
encountered.
R
R2 R2 a R1 = i-Pr R2 = p-Tol
N N b R1 = i-Pr R2 = p-Anisyl
N N c R1 = CH2Ph R2 = p-Anisyl
Pt
R1 R1 d R1 = CH2Ph R2 = p-Anisyl
Cl
29
N N
N N
N Ru N Ru N
N N
N N
30 32
2+
N N
N N
N Ru Ru N
N N
N N
31
3MC
3MC
DE DE
3MLCT
3MLCT
hn knr
hn knr
Fig. 19 Schematic illustration of the influence of cyclometallation on the energies of MLCT and
MC states
(PF6)2 PF6
N PF6 N PF6
N N N N
Ru Ru
N N
N N N
N N N N
N N
Ru Ru
N N N
N
CO2H CO2H HO2C
33 CO2H 35 CO2H
34 36
Fig. 20 Photocurrent action spectra of 33–36 in a TiO2 solar cell using 0.5 M LiI and 0.05 M I2 in
g-butyrolactone as electrolyte, with the performance of N719 shown for comparison (reprinted
with permission from [52] # 2010 American Chemical Society)
As seen above, dpyb binds as an NCN-coordinating ligand to Ru(II) and Os(II) ions,
cyclometallating at position 2 of the benzene ring. In contrast, reaction of dpybH
with hydrated iridium(III) chloride gives products in which the ligand metallates at
position 4 of the central ring: the ligand is thus bound in a bidentate fashion, with
one pendant, uncoordinated pyridine ring (N^C binding mode, Fig. 21) [55]. It
seems that metallation at C4 is kinetically favoured over C2. A similar pattern of
reactivity has been observed for palladium(II), at least when Pd(OAc)2 is used as
the metal source [56].
112 G.R. Freeman and J.A.G. Williams
5 5
4 M
6 4 6
1 3 1 N N N N
3
2 2 N N
N N N
M
N^C binding mode 45
N^C^N binding mode
N N
38
Blocking of the C4 and C6 position of dypbH with substituents such as CH3, CF3
or F successfully directs the metallation to position C2, allowing NCN-coordinated
Ir(III) complexes to be obtained. The initial products formed upon reaction with
IrCl33H2O are chloro-bridged dimers of the form [Ir(NCN)Cl(m-Cl)]2 (e.g. 37,
Fig. 22), which can be cleaved by a variety of ligands to generate mononuclear
complexes [57].
Another way to induce the NCN binding mode is to use the C3 symmetric
proligand 1,3,5-tris(2-pyridyl)benzene (38, Fig. 21): all three C–H bonds in this
compound are equivalent, so the question of regiochemistry does not arise.
A representative selection of the NCN-coordinated mononuclear complexes of
varying charge that can be obtained via the intermediacy of the chloro-bridged
dimer, 37, obtained from 1,3-bis(2-pyridyl)-4,6-dimethylbenzene (dpyxH), is
illustrated in Fig. 22. Reaction with terpyridines leads to dicationic complexes
such as [Ir(dpyx)(ttpy)]2+, 39, the Ir(III) analogue of the Ru(II) complex 30
discussed in Sect. 5.1. Dimetallic complexes of the type [{Ir(dpyx)}2(m-tpy-fn-
tpy)]4+ (n ¼ 0–2), 40, comparable to the Ru dimer 31, can be isolated upon reaction
of 37 with back-to-back bridged terpyridines [58]. If a bipyridine is used rather than
a terpyridine, only two of the three chloride ligands around the metal are displaced,
leading to monocationic complexes of the type [Ir(dpyx)(bpy)Cl]+, 41.
Iridium(III) has a higher propensity to undergo cyclometallation than ruthenium
(II): Ir(III) complexes incorporating two or three metallated carbon atoms in the
coordination sphere are common [2], whereas Ru(II) is typically limited to mono-
cyclometallation. In the present instance, further cyclometallating ligands can
readily be introduced. For example, reaction of 37 with 6-phenyl-2,20 -bipyridine
(phbpyH) leads to [Ir(dpyx)(phbpy)]+, 42, a doubly cyclometallated bis-terdentate
complex featuring cis-C2N4 coordination [59]. Such complexes are terdentate
analogues of the well-known class of cationic tris-bidentate iridium complexes of
which [Ir(N^C-ppy)2(N^N-bpy)]+ is the archetypal example [60]. They display
electrochemical properties quite similar to those of [Ru(bpy)3]2+, viz. reversible
first oxidation and reduction waves at accessible potentials (Fig. 23), rendering
them of interest for a variety of applications such as light-emitting electrochemical
cells and photosensitisers for “water splitting” [61].
Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and. . . 113
Ir
N N
[Ir(dpyx)(dppy)]
43 +
N N
Cl dppyH2 Cl
N
Ir Ir
N N AgOTf N
N
no solvent
bpy
ppyH
AgOTf
[Ir(dpyx)(ppy)Cl]
HO OH [Ir(dpyx)(bpy)Cl]+
Cl
44 no solvent N N
Ir 41
Cl
Cl
Ir
N N
Cl 2+
+ phbpyH ttpy
N HO OH
37
HO OH
N N
Ir
N N N N
Ir
tpy–(F)n–tpy N N
HO OH
+
[Ir(dpyx)(phbpy)]
4+
42 [Ir(dpyx)(ttpy)]2+
N
N N
N 39
Ir N N Ir
N n N
N N
n=0–2
40
Fig. 22 Structures of a range of Ir(III) complexes containing the NCN-bound dpyx ligand,
obtained through the intermediacy of the chloro-bridged dimer 37
Fig. 23 Cyclic voltammogram of 42 in CH3CN at 298 K, at a scan rate of 300 mV s1. The insets
show the redox processes at a series of scan rates (50, 100, 200, 300, 400, and 500 mV s1); the
reversibility of each process is confirmed by the linear dependence of the current on the square root
of the scan rate
trans to one another, and are therefore labilised, due to the high trans influence of
cyclometallated carbon atoms. The result is that [Ir(dpyx)(dppy)] has poor stability
in solution, particularly in the presence of light, under which conditions one of the
two trans-disposed Ir–C bonds is cleaved, and the sixth coordination site probably
occupied by a weakly bound solvent molecule. It is interesting to note that no such
instability is observed for complexes of the type [Ir(dppy)(NNN)]+, despite their
having the same arrangement of trans Ir–C bonds [63]. Evidently, the ligand field
states through which Ir–C dissociation occurs in [Ir(dpyx)(dppy)] are destabilised
by the presence of the third cyclometallated carbon. 2,6-Bis(2-benzimidazolyl)
pyridine has similarly been used recently as a “pseudo-biscyclometallating” ana-
logue of dppy, involving deprotonation of the benzimidazole rings to give a
dianionic ligand [64].
If a bidentate cyclometallating ligand, such as ppy, is used in place of dppy, then
a chloride ligand remains in the sixth site, e.g. [Ir(dpyx)(ppy)Cl], 44. Being trans to
the Ir–C bond, the Ir–Cl does show some lability, but the rate of dissociation is
much slower than that observed for [Ir(dpyx)(dppy)]. Moreover, the chloride can be
replaced by stronger field, acceptor ligands such as CN, which increase the
stability.
Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and. . . 115
Fig. 24 Simplified schematic energy level diagram showing the influence of cyclometallation
on the frontier orbitals in bis-terdentate Ir(III) complexes containing NCN-coordinated
dipyridylbenzene ligands, leading to excited states of different character. A and B represent the
two different ligands [11]
The introduction of a second cyclometallating carbon atom into the other ligand,
as in 42, raises the energy of metal-centred orbitals, and reduces the LLCT
character, both of which lead to an augmentation in the radiative rate constant.
Filled metal and ligand orbitals probably become quite comparable in energy in this
case, with the LUMO being localised on the NN part of the NNC ligand, leading to
higher MLCT character to the excited state. Indeed, these complexes emit quite
efficiently in the orange-red region of the spectrum, with quantum yields of around
2–6 % according to the substituents, comparable to [Ru(bpy)3]2+ and [Ir
(ppy)2(bpy)]+ derivatives [59]. Finally, the introduction of a third cyclometallating
carbon atom, as in 43, or an anionic chloride as in 44, raises the energy of the metal
orbitals further, leading to unequivocal MLCT character. Indeed, complex 44 is
very highly emissive in degassed solution at room temperature: Flum ¼ 76%,
t ¼ 1.6 ms, lmax ¼ 508 nm in CH3CN. OLEDs employing 44 or its derivatives as
triplet-harvesting dopants show high efficiencies, competitive with many of the best
iridium emitters reported to date. Haga and co-workers have also obtained similar,
highly efficient emitters in their work using 1,3-bis(N-methyl-benzimidazol-2-yl)
benzene (45, Fig. 21) as an NCN ligand [68]. Interestingly, in that case, no C4/6
blocking groups are required in the central ring: NCN rather than NC coordination
is observed with the parent ligand.
An interesting feature of cyclometallation is that it is accompanied by an increase
in the electron density within the metallated aryl ring, particularly at the position
para to the site of metallation. The propensity of the ring to undergo electrophilic
aromatic substitution reactions is thus enhanced selectively at this position [69].
This feature can be put to use for introducing functionality into a ligand post-
complexation, rather than into the ligand prior to complexation. For example, [Ir
(dpyx)(ttpy)]2+, 39, undergoes bromination under mild conditions (NBS in MeCN at
room temperature) specifically at the para position of the central ring of dpyx.
Naturally, in the case of the bis-cyclometallated complex [Ir(dpyx)(phbpy)]+, 42,
the lateral phenyl ring of the NNC ligand undergoes a comparable reaction. The
modified system [Ir(dpyx)(mtbpy-f-Br)]+ (46, Fig. 25) has been developed as a core
for linear stepwise expansion along the Cdpyx–Ir–Nphbpy axis, through an iterative
sequence of cross-coupling with a boronic acid-substituted substrate (a purely
organic compound or a metal complex), in situ bromination, and a second cross-
coupling [59, 70]. The bromination step occurs specifically at the dpyx ligand,
because the corresponding reaction at the phenyl ring of the NNC ligand is blocked
by the presence of the methyl group. Using this strategy, a variety of linearly
elaborated mononuclear complexes and heterotrimetallic systems have been created
in a controlled regiospecific manner. With regard to such multimetallic systems, it
should be noted that bis-terdentate complexes offer structural advantages over those
with bidentate ligands, because the latter, normally having D3 or C2 symmetry, are
chiral, whereas the former (normally D2d symmetry) are not. When two or more
chiral complexes are linked together, mixtures of diastereoisomers are formed
unless the starting mononuclear complexes are resolved first.
It is, however, possible to prepare chiral complexes with terdentate ligands, if the
ligand is desymmetrised, i.e. comprising different lateral groups on either side of the
central ring. An elegant example comes from the group of Haga, who were able to
Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and. . . 117
+ n+
N (HO)2B N
N N
Ru N Br Ru N
N Pd(0) cat. N
46
NBS, MeCN
n+
n+ N
N
N Br Ru N
N
N
Ru N
N
B(OH)2
Pd(0) cat.
resolve complex 47 into its two enantiomers, as confirmed by their equal but opposite
circular dichroism spectra (Fig. 26, top) [71]. More unusually for transition metal
complexes, circularly polarised luminescence spectra could also be recorded (Fig. 26,
bottom).
N
N N N N N
Pt Pt Pt
Cl Cl Cl
48 49 50
118 G.R. Freeman and J.A.G. Williams
40
Δε / M-1cm-1 20
-20
-40
250 300 350 400 450 500 550
Wavelength / nm
3
1
CD / mdeg
-1
-2
-3
450 500 550 600 650
Wavelength / nm
Fig. 26 Circular dichroism spectra (top) and circularly polarised luminescence spectra (bottom)
of the two enantiomers of complex 47 resolved by HPLC on a chiral column. Solvent ¼ CH2Cl2
(reprinted with permission from [71] # 2009 Royal Society of Chemistry)
Fig. 27 Showing how the emission spectra of the Pt(dpyb)Cl class of complex can be tuned from
that of the parent 48 (third from left), either to longer wavelengths through the introduction of
electron-donating substituents at the 4-position, or to shorter wavelengths using electron-
withdrawing groups at this position/substituents in the pyridyl rings. Spectra are recorded in
CH2Cl2 at 298 K; lex ¼ 400 nm; intensities have been normalised
bidentate ligands with respect to distortion from D4h to D2d symmetry in the excited
state has long been recognised as a potential sink for the excited-state energy [3, 12].
As far as the pair of terdentately bound complexes are concerned, it has been noted
that the Pt–C bond is significantly shorter (ca. 1.90 Å vs. 2.05 Å) in the NCN
complex than in the NNC analogue, which may ensure a stronger ligand field and
hence displacement of the deactivating d–d states to higher energy [72]. However, a
recent comparison of these systems by TDDFT suggests that the key point is the
greater rigidity of the former, with a lower degree of reorganisation in the excited
state compared to the ground state [76].
The emission energy of complexes of this type can be tuned over a wide range,
without significantly compromising the quantum yields, by introducing substituents
into the cyclometallated aryl ring or into the pyridine rings. Electron-releasing
substituents in the central 4-position of the benzene ring lead to increasingly red-
shifted emission according to their electron-donating ability, e.g. lmax increases in
the order R ¼ CO2Me < H < mesityl < Me < 2-pyridyl < 4-tolyl < 4-biphenylyl
< 3,4-dimethoxyphenyl < 2-thienyl (Fig. 27) [77]. There is a good correlation
between the emission energy and the oxidation potentials Epox of the complexes,
with a slope of 4,900 cm1V1, whereas the reduction potentials vary little with the
4-substituent. The obvious inference is that the substituent influences primarily the
HOMO, such that the observed red shift with increasing electron-donating ability
reflects an increase in the HOMO level and a LUMO that remains essentially
unchanged. TDDFT calculations support this picture, revealing a major contribu-
tion to the HOMO but not to the LUMO (Fig. 28a) [78]. The LUMO, in contrast, is
localised predominantly on the pyridyl rings, and it may be noted that the 40 -
position makes no contribution to the HOMO. Thus electron-donating substituents
in this position are expected to increase the LUMO level without significantly
120 G.R. Freeman and J.A.G. Williams
Fig. 28 Frontier orbital diagrams for Pt(dpyb)Cl 48 (a) and the derivative 51 incorporating a 4-
(N,N-dimethylamino)phenyl group at the 4-position (b), calculated by TDDFT including CH2Cl2
as the solvent
affecting the HOMO and, indeed, substituents such as methoxy groups in these
positions have been found to blue-shift the emission [79, 80].
For the complex with the strongly electron-donating pendant R ¼ C6H4NMe2,
51 (Fig. 28b), the emission energy is substantially lower than what is predicted on
the basis of the Eem vs. Epox correlation. Moreover, the emission band for this
complex in CH2Cl2 is broad and structureless, and displays a high degree of positive
solvatochromism, in contrast to the other systems whose spectra are structured and
whose energies are insensitive to the solvent. This behaviour is thought to be due
to a switch in the nature of the lowest-energy excited state from p–p* to one
of primarily intraligand charge transfer (ILCT), akin to the behaviour of
donor–acceptor molecules such as 4-(dimethylamino)benzonitrile. TDDFT
calculations support this notion (Fig. 28b), showing the HOMO to be largely
localised on the pendant group, with the LUMO on the NCN moiety. Reversible
switching from the ILCT to the p–p* state can be induced by protonation of the
amine, both forms being highly luminescent (F ¼ 0.46 and 0.40, respectively), but
with significantly different spectra (Fig. 29) [77, 78]. The effect has been extended
to azacrown-ether-appended complexes, in which a similar switching is observed
upon complexation of divalent metal ions such as Ca2+ to the macrocycle, which
bind to the N lone pair in a comparable way to H+ [78].
Pyrazole is a more electron-rich heterocycle than pyridine. Thus on the basis of the
HOMO–LUMO description above, one might anticipate that a pyrazolyl-based Pt
(NCN)Cl complex should display blue-shifted emission compared to Pt(dpyb)Cl.
However, the bite angle offered by the NCN system will change on going from dpyb
to dpyzb {dpyzbH ¼ 1,3-bis(1-pyrazolyl)benzene}, and may be less well suited for
Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and. . . 121
Energy
1LC
1LC
3TICT
3LC 3LC
3TICT
H+
S0 S0
Fig. 29 Left: Emission and excitation spectra of 51 in CH2Cl2 (6 105 M) at 298 K (solid lines)
and the corresponding blue-shifted spectra after addition of trifluoroacetic acid (102 M) (dotted
lines). Right: A schematic illustration of the effect of protonation of the amine on the relative
energies of the intraligand charge transfer (TICT) and NCN-centred (LC) excited states
Fig. 30 Mononuclear (52) and trinuclear (53) complexes of platinum with 1,3-bis(1-pyrazolyl)
benzene, and a complex of 1,3-bis(8-quinolyl)benzene featuring 6-membered chelate rings, 54.
The structure of 53 is reprinted with permission from [81] # 2008 American Chemical Society
binding. Indeed, Connick and co-workers observed that reaction of dpyzbH with
K2PtCl4 can give either the terdentately bound Pt(bpyzb)Cl, 52a {the analogue of Pt
(dpyb)Cl, 48} or a trimer [Pt(m-dpyzb)Cl]3, 53 (Fig. 30), in which each ligand is
bound N^C-bidentate with one metal, with the second pyrazole ring bridging to a
second platinum centre [81]. In an independent study, Williams and co-workers
found that the former binding mode is promoted over the latter by substituents as
small as a methyl group at the 4-position of the benzene ring [82]. They investigated
the emission characteristics of complexes such as 52b. The emission of 52b was
indeed found to be substantially blue-shifted compared to that of Pt(dpyb)Cl, as had
been predicted. However, the quantum yield drops by a factor of 30, and this again
seems to be associated with the inferiority of dpyzb as a ligand. From the large shift
in the emission spectrum of 52b on cooling to 77 K, it is evident that the excited state
of this complex suffers from more distortion than that of Pt(dpyb)Cl.
122 G.R. Freeman and J.A.G. Williams
Fig. 31 Illustrating the control over the excimer energy that can be achieved in the Pt(dpyb)
Cl class of complex through the introduction of substituents into the pyridyl rings
Fig. 32 Photomicrographs taken between cross polarisers (top) and emission spectra (bottom) of
the chloroplatinum complex of 1,3-[5-(3,4,5-trihexyloxyphenyl)pyridin-2-yl]benzene (a) fast
cooled from the LC phase after the texture is developed, and (b) fast cooled from the isotropic
phase (reprinted with permission from [90] # 2008 Wiley-VCH)
a
2.1 eV
2.6 eV 2.8 eV
3.2 eV
Ca
TPD:PC
CBP
CBP:OXA:
ITO
OXA
36
4.9 eV
5.4 eV
6.0 eV
7.0 eV
b
08 e
d
ba c 0.6 a c
1.0
y 0.4 b J
0.2
0.5 0.0
0.0 0.2 0.4 0.6 08
EL intensity [a.u.]
0.0
d e
1.0 J
0.5
0.0
500 600 700
Wavelength [nm]
Fig. 33 Devices of the structure shown in (a) prepared using the Pt(dpyb)Cl class of complex
within the emitting layer (6 % by mass) display the emission spectra shown in (b). The
corresponding CIE coordinates are shown in the inset. Compounds are Pt(dpyb)Cl (a), and
derivatives with 4-substituent ¼ CO2Me (b), Me (c), mesityl (d), pyridyl-2-yl (e), and
C6H4NMe2 (f) (reprinted with permission from [92] # 2007 Wiley-VCH)
intensity between the monomer and excimer regions. Kalinowski and co-workers
have shown that the problem can be overcome by ‘filling in’ this region with
emission from an exciplex. A WOLED with a colour rendering index of 90 and
an external quantum efficiency of 6.5 % has been produced in this way [100]. The
use of derivatives with blue-shifted excimers offers another strategy for achieving
this goal. The reader is directed to a recent comprehensive review on the subject for
a more detailed description of this work [101].
Finally, we note that complexes of this type are attracting interest in the fields of
biosensing and imaging. Luminescent oxygen sensors [102] and probes of protein
binding [103, 104] have been developed. Pt(dpyb)Cl has also been used to
126 G.R. Freeman and J.A.G. Williams
Fig. 34 Time-resolved gated emission images of CHO cells incubated with Pt(dpyb)Cl, 48. The
images were recorded after 355 nm laser excitation at the time delays shown between 100 and
2,900 ns after the laser flash. The time gate used was 100 ns, exposure time 20 ms, five
accumulations per time delay. Scale bar: 50 mm [105]
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Top Organomet Chem (2013) 40: 131–174
DOI: 10.1007/978-3-642-31081-2_5
# Springer-Verlag Berlin Heidelberg 2013
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
2 PCP Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
2.1 Complexes Based on the Archetypal 1,3-(CH2PR2)2-C6H3 Ligand Backbone . . . . . 134
2.2 Reactivities of (PCP)Ni Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
2.3 PCsp3P Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
1 Introduction
It is a long-established fact that chelating ligands greatly influence the stability and
reactivities of transition metal complexes. Among the numerous types of chelating
ligands used to control the reactivities of organometallic complexes, terdentate
pincer ligands stand out for their ability to bestow high stability and enhanced
reactivities to many transition metals. Since their initial introduction in the late
1970s by the groups of Shaw [1] and van Koten [2, 3], pincer complexes have
evolved into a diverse class of compounds possessing highly desirable practical
applications in addition to displaying rare or unprecedented structural/bonding
features that have challenged our fundamental notions of metal–ligand interactions.
A survey of the pincer literature indicates that bulk of the reports appearing to
date concern complexes of noble metals, whereas complexes based on their 3d
analogues—Fe, Co, and Ni—have received much less attention. Of the latter
metals, pincer complexes of nickel were among the first pincer complexes reported
by Shaw [1] and their chemistry is more developed. This is especially true for
complexes based on the 1,3-bis(aminomethyl)phenyl ligands introduced and devel-
oped by van Koten’s group. The chemistry of these so-called NCN-type complexes
(Fig. 1) has been studied extensively over the past 3 decades, whereas the
organonickel chemistry of complexes based on the original PCP-type ligands
introduced by Shaw’s group has developed over the last decade.
This chapter will review the chemistry of nickel complexes featuring ECE-type
pincer ligands possessing the common feature of a covalent C–Ni linkage at the
central position of the pincer ligand. The discussion will focus on the synthesis,
characterization, and reactivities of nickel complexes based on both symmetrical
and unsymmetrical ligands, ECE and ECE0 , composed of an anionic hydrocarbyl
moiety flanked by two neutral donor moieties such as phosphine, amine,
phosphinite, thioether, and N-heterocyclic carbene. Pincer-type nickel complexes
based on a nonhydrocarbyl linker moiety (e.g., ENE, ESiE, etc.) do not fall within
the scope of this review; readers interested in the chemistry of these systems are
ECE-Type Pincer Complexes of Nickel 133
PR 2 NR 2 O PR 2 NR 2 SR
Ni X Ni X Ni X Ni X Ni X
PR2 NR2 O PR2 O PR2 SR
H
PR 2 O PR2 N PR2 N NR
Cl
Ni X Ni X Ni X Ni X
P O P HN P N NR
R2 R2 R2
encouraged to consult the primary literature and other reviews of pincer complexes
[4–11]. We have strived to cite all pertinent literature on (ECE)Ni complexes
reported over the period 1976–2011; any omission is unintentional. To our knowl-
edge, this is the first review covering solely the chemistry of pincer complexes of
nickel.
The discussion is organized into five main sections representing the various
families of (ECE)Ni complexes based on the type of pincer ligand featured in
them. Presentation of the different sections reflects the chronological order in
which the target complexes appeared in the literature. Thus, the bis(phosphine)-
and bis(amine)-type complexes that were introduced in the 1970s and 1980s,
respectively, will be presented first, followed by the recently introduced complexes
featuring phosphinite, phosphinimine, thioether, and N-heterocyclic carbene donor
moieties. The following rules of nomenclature have been applied to designate the
various types of pincer ligands discussed here: bis(phosphine)- and bis(amine)-
based pincer ligands are referred to as PCP and NCN ligands, respectively; the
symmetrical ligands based on bis(phosphinite), bis(phosphinimine), bis(thioether),
and bis(N-heterocyclic carbene) moieties are referred to, respectively, as POCOP,
PNCNP, SCS, and ĈCĈ; the POCN and PNCN designations will be used to refer to
the unsymmetrical phosphinite/amine or phosphinimine/amine ligands. Where
appropriate, the unmetallated state of the ligand will be denoted by inserting an
“H” or a halide next to the “C” in the ligand designation, for example, PCHP or
NCBrN. Moreover, hybridization of the carbon atom will always be indicated for
ligands featuring an sp3 hydrocarbyl moiety, for example PCsp3P or POCsp3OP, but
not for ligands based on an aryl or vinyl moiety; the latter constitute a majority
among the pincer ligands used to date and so the hybridization of the nickellated
carbon in these compounds will only be specified when emphasis of this feature is
called for in the context of the discussion. Finally, where necessary, the N- or P-
substituents will be denoted as a superscript next to the donor atom, for example
(NCNMe). Some of the main types of complexes discussed in this review are
illustrated in Fig. 1.
134 D. Zargarian et al.
2 PCP Complexes
P Cl
P= PCy 2 P Cl Ni
Cl P
Ni
Cl P
this orange–yellow complex into a sparingly soluble purple solid that was identified
as the nonnickellated, 2:2 adduct {trans-(m kP, kP0 -PCHPCy)2Ni2Cl4} (Fig. 2)
[15]. These observations are in stark contrast to the facile nickellation of PCHPCy
when reacted with [Ni(H2O)6]X2 in refluxing EtOH (X ¼ Cl, Br; vide infra).
Interestingly, the non-metallated 2:2 adduct could not be made to undergo
nickellation, raising the question of whether such nonmetallated species are
intermediates en route to metallation, or mere side-products.
Shaw’s first report also described the preparation of a few derivatives of (PCPt-Bu)
Ni, including the cyano and phenylalkynyl derivatives and the cationic CO adduct;
the latter was reportedly prepared by reacting (PCPt-Bu)NiCl with NaBPh4 and CO in
EtOH. It should be noted that this report provides the characteristic IR band for the
phenylalkynyl derivative (n(CC) ~ 2,075 cm1), but the corresponding data for
the cyano or carbonyl species, n(CN) and n(CO), respectively, were not
reported. The preparation of (PCPt-Bu)NiH was also attempted by reacting the
corresponding chloride complex with NaBH4 in refluxing EtOH. The anticipated
high-field signal for the Ni–H moiety was not observed in the 1H NMR spectrum of
the product, but its IR spectrum showed a showed a metal-hydride-like stretching
frequency at ~1,757 cm1. As will be described below, the reaction of (PCPt-Bu)NiCl
with NaBH4 has been revisited recently and shown to lead to the initial formation of
(PCPt-Bu)Ni(BH4), which might explain why Moulton and Shaw could not detect the
signals due to a terminal hydride in the NMR and IR spectra.
Other interesting observations noted in Shaw’s original report touch on the
generally high thermal stability of PCP complexes and the fact that PCHP ligands
appear to be metallated more readily with nickel compared to Pd and Pt. For
instance, the synthesis of (PCPt-Bu)PtCl yielded a nonmetallated side-product that
was formulated as [(PCHP)PtCl2]n (n > 2); prolonged heating of this species did
not give the desired metallated product.
Although (PCP)Ni complexes were among the first pincer complexes of nickel
to be introduced, the chemistry of these complexes remained essentially dormant
over the 2 proceeding decades. Indeed, the pincer chemistry of nickel during the
1980s and most of the 1990s was dominated by the (NCN)Ni chemistry developed
by van Koten’s group (vide infra). The only reports of PCP-type nickel complexes
appearing in the 1990s concerned the structural characterization of (PCP)Ni(halide)
complexes (vide infra) [17] and their use in preparation of metallodendrimeric
136 D. Zargarian et al.
O P= PPh2
P P
R
Ni O Ni O O
P P O O=
O O
P
P + CO P P= i-Pr 2P
2 Ni OH Ni O Ni
P - H 2O P
O
P
+ 2 H2 O - 2 NH3
P + PhC(H)O P P
2 Ni NH 2 Ni N + Ni OH
P - NH 3 P H P
Ph
In spite of this solution fluxionality, the solid state structure shows that the
o-semiquinone ligand binds the Ni center in an unsymmetrical fashion: the basal
O atom bearing the negative charge makes a shorter Ni–O distance, while the apical
O atom bearing the single electron forms a longer Ni–O distance. These
observations can be justified by invoking the repulsive interactions between the
dz2 and pz hybrid orbitals with the ligand orbital bearing the single electron.
Cámpora’s group has introduced a number of interesting (PCPiPr)NiX
complexes that show how this ligand frame allows the isolation of rare and reactive
derivatives [26, 27]. The precursor (PCPiPr)NiBr was prepared by reacting Ni
(COD)2 with 1-Br-2,6-(i-Pr2PCH2)2-C6H3 (80 C) and reacted with NaOH or
NaNH2 (in THF and under sonication) to give (PCPiPr)Ni(OH) and (PCPiPr)Ni
(NH2), respectively. It is interesting to note that the analogous Pd–NH2 complex is
much less stable and could not be isolated. (PCPiPr)Ni(OH) reacts with CO to give
the unusual CO2-bridged species {[(PCPiPr)Ni]2(m,kC,kO-CO2)} (Fig. 4); this
compound displays a very characteristic 13C NMR signal for the m-CO2 (tt,
206 ppm, 3JP–C ~ 21 and 6 Hz). (PCPi-Pr)Ni(NH2) reacts readily with water or
MeOH to generate ammonia and the analogous Ni–OH and Ni–OMe derivatives;
the latter was characterized by crystallography. The nucleophilicity of the amido
moiety is apparent from the facile reaction with benzaldehyde that generates the
corresponding aldimido and hydroxy complexes (PCPiPr)Ni(N ¼ CHPh) and
(PCPiPr)Ni(OH), in addition to ammonia (Fig. 4).
The above species have been characterized convincingly by 1H NMR (e.g., a
triplet at 2.59 ppm, 3JP–H ~ 6 Hz, for the Ni–OH proton; a triplet at 1.00 ppm,
3
JP–H ~ 8 Hz, for the Ni–NH protons), IR (e.g., n(O–H) ~ 3,600 cm1;
(n(N–H) ~ 3,355 and 3,295 cm1), and X-ray diffraction studies. The hydroxo
complex is a monomer in solution, as established by cryoscopic measurements,
but in the solid state two discrete molecules are paired up through O H CMe2
interactions to produce a suprastructure. The Ni–NH2 derivative is a monomer in
the solid state showing a fairly short Ni–N bond distance (ca. 1.87 Å). A compari-
son of the fairly similar Ni–C bond distances in (PCPi-Pr)NiX (ca. 1.92 Å for
X ¼ Br [28], OH, OMe, and NH2) implies fairly similar trans influences for these
X ligands.
138 D. Zargarian et al.
P P
*
Ni Cl P= PPh2 Cl Ni Cl
P P
The reactivities of (PCPt-Bu)NiR have not been explored extensively, but recent
reports have identified reactions of potential promise. For example, Hazari’s group
ECE-Type Pincer Complexes of Nickel 139
W O
P OC CO P C
H CO
Ni H Ni H H W
190 K C
P P O C
O
P= t-Bu2P O O
P C C
- H2
> 230 K
Ni O C W
has reported the insertion of CO2 into Ni–R bonds in (PCPt-Bu)Ni–R (R ¼ H, Me,
Z1 allyl) [37]. This study has shown that the rate of CO2 insertion varies as a
function of the R moiety, proceeding at r.t. over minutes for Ni–H or hours for
Ni–allyl, but requiring extensive heating at 150 C for Ni–Me. DFT studies have
shown that the formate derivative resulting from CO2 insertion into Ni–H is much
less stable than the corresponding products with the Ni–Me and Ni–allyl precursors,
which explains why only the insertion into the Ni–hydride complex is reversible.
Reversible insertion of CO2 has also been observed with (POCOPt-Bu)NiH; in this
system, CO2 can be reduced to methanol in the presence of catecholborane (vide
infra). DFT studies of the PCPt-Bu system also suggest that the insertion reaction
involves a concerted, 4-centered mechanism involving the Ni–H and one of the
C¼O moieties, whereas in the case of the methyl and allyl derivatives the insertion
follows a path involving interaction between the CO2 and the R moieties only, with
Ni playing a spectator role.
A recent report by Peruzzini’s group describes the reactivities of (PCP)NiH
complexes and underlines the general ability of pincer complexes to stabilize
unstable species and highly unusual bonding arrangements [38]. This report has
shown that the “hydridic” Ni–H moiety in (PCPt-Bu)NiH reacts with protic acids to
generate H2. Protonation with the strong acid HBF4 was rapid, whereas the reaction
with CF3CH2OH was found to go through an observable intermediate featuring
NiH HOCH2 CF3 type interactions (DH ¼ 2.5 kcal/mol) as evidenced by
the following observations: IR spectrum of the mixture showed a lowering of
n(O–H) frequency, whereas the 1H NMR spectrum showed the downfield displace-
ment of the NiH signal from 9.77 ppm to ca. 0.25 ppm. The reaction with the
“acidic” tungsten hydride species CpW(CO)3H allowed observation of unusual
intermediates featuring a m,Z1:1–H2 moiety and isolation of the very rare species
Bu
½CpW(COÞ2 ðm; kC ; kO CO Ni(PCPt Þ (Fig. 6).
Relative to terminal CO ligands, the “isocarbonylic” ligand bridging Ni and W
centers displays a somewhat longer C–O bond (ca. 1.20 vs. 1.15 Å) and a some-
what shorter W–C bond (ca. 1.91 vs. 1.92 and 1.96 Å), implying significant
p-backbonding from both metal centers. The W–C–O–Ni arrangement is fairly
140 D. Zargarian et al.
P H P P H
H
Ni H B Ni H Ni B
P H P P H H
H B H
excess H H
BH3 .THF NaBH4
P P
Ni H P= t-Bu2P Ni Cl
P P
excess
P BF3 .Et2 O P H 2O P H
Ni F Ni F F Ni O F F
P P B P H
F B F
F F
linear and the Ni–O distance is ca. 1.97 Å. Interestingly, while three distinct signals
are observed in the solid state 13C CPMAS NMR spectrum for the three different
CO ligands (d 224, 229, and 240), the solution spectrum shows only one signal at d
224, implying a dynamic exchange process.
Another recent report from Peruzzini’s group describes new examples of unusual
“cation-like” species being stabilized by the PCPt-Bu ligand [39]. This report
explores the reactivities of the Lewis acids BH3 and BF3 with the isolobal Lewis
bases H and F coordinated to [(PCPt-Bu)Ni]+. Monitoring the reaction of (PCPt-Bu)
NiH with BH3·THF at 190 K showed the formation, over 8 h, of (PCPt-Bu)Ni(BH4)
(11B NMR: 33 ppm, t, 1JB–H ~ 82 Hz), but this species was not stable to isolation,
yielding instead the starting hydride species (Fig. 7). The same BH4 species could be
obtained by reaction of (PCPt-Bu)NiCl with NaBH4, a reaction reported more than 3
decades earlier by Shaw in the attempt to prepare the hydride species (vide supra).
Combined DFT and 1H{11B} NMR studies of D-labeled (PCPt-Bu)Ni(BH4) have
revealed that an isotopomeric mixture forms as a result of facile H/D exchange via
intermediates of the type (PCPt-Bu)Ni(2-kH:kD-BHxD4x).
The analogous reaction between BF3·THF and (PCPt-Bu)NiF, prepared from the
corresponding chloride and five equivalents of thallium fluoride, led to facile
formation of (PCPt-Bu)Ni(BF4), which was characterized unambiguously from the
broad quintet in the 31P NMR spectrum (JP–F ~ 8 Hz) and the characteristic broad
19
F NMR signal for coordinating BF4 anion (ca. 178 ppm). The same product was
also obtained by reacting the corresponding chloro precursor with AgBF4. Both
synthetic routes also gave the cationic aquo adduct [(PCPt-Bu)Ni(OH2)][BF4] as a
minor side-product (19F NMR: 157 ppm); the latter was also the only species that
could be isolated from both reaction mixtures (Fig. 7). Solid state structures of the
fluoro and aquo derivatives showed “normal” bond distances for Ni–F (1.87 Å) and
Ni–O (1.96 Å); two fluorine atoms of the BF4 anion were found to interact with one
H atom of the aquo ligand. The crossover experiments (Ni–F + BH3 and Ni–H +
BF3) gave the same mixture of products arising from H/F scrambling
ECE-Type Pincer Complexes of Nickel 141
P NiI2 , EtOH P C6 H6 P
Me Ni I Ni I
P 130 °C, - HI P 180 °C P
P NiI2 O P
OMe Ni I
P EtOH, 130 °C P
(Ni–H. . .BF3, Ni(BH4), and Ni(BF4)). It is worth adding here that a very similar
“cation-like” Ni–BF4 species as well as cationic Ni–OH2 species have been
prepared with the PCsp3P ligand; moreover, the cation [(PCPi-Pr)Ni(NCMe)]+ has
been prepared and shown to be a good promoter for Michael-type hydroamination
of acrylonitrile. These results are described in the PCsp3P section below.
X
P P= t-Bu2P P
Ni X + X Ni
P NiX2, Toluene P P(CH2 )5 PH
reflux, 12 h X
+ [NiX4][PH(CH 2) 5PH]
NiBr2
Toluene P= i-Pr 2P
25-80 °C, 2 h
P P Toluene, DMAP P
Br Br
Ni Ni Ni Br
Br Br reflux P
P P
P n-BuLi P PhSiH 3 Ph
Ni X Ni H Si
P P - H2 n
H
P= t-Bu 2P
P= i-Pr 2P
P + HX P
Ni R Ni X
P - RH P
Charge neutral alkyl, phenyl, and alkynyl derivatives (PCsp3Pi-Pr)NiR are more
accessible than their analogous PCsp3Pt-Bu counterparts [28]. For instance,
(PCsp3Pt-Bu)Ni-(n-Bu) is much less stable than its PCsp3Pi-Pr analogue, undergoing
facile b-H elimination to generate (PCsp3Pt-Bu)NiH. This hydride species could not
be isolated, because it is thermally unstable toward reductive elimination, but it was
identified by the characteristic upfield triplet in 1H NMR (10 ppm; 2JP–H ¼ 53 Hz)
[41]. (PCsp3Pt-Bu)NiH is inert toward olefins and alkynes, but can promote the
oligomerization of phenylsilane (Fig. 10).
As anticipated, Ni–C bond distances in (PCsp3Pi-Pr)NiR vary according to the
hybridization of the carbon atom (Ni–Csp < Ni–Csp2 < Ni–Csp3) [28]. Moreover,
all of these distances are longer than the mean values reported in the literature for
the corresponding Ni–C distances in comparable complexes, reflecting the strong
trans influence of the metallated central carbon of pincer ligands. The observed
thermodynamic trend partially mirrors the kinetic stabilities of Ni–R moieties in the
protonolysis reaction with phenylacetylene to generate RH and (PCPi-Pr)Ni
(CCPh). Thus, the Ni–Me and Ni–Bu derivatives reacted with phenylacetylene
at room temperature, whereas the Ni–CCMe derivative required heating to
undergo protonolysis and the Ni–Ph derivatives did not react even at higher
temperatures. Similar protonolysis reactivities were observed when HCl or HBF4
was used instead of PhCCH (relative rates: Ph < CCMe < Me; Fig. 11) [44]. It is
not known whether these protonolysis reactions proceed via a concerted, constant-
oxidation-state process or in a step-wise fashion, beginning with oxidative addition
of the alkynyl C–H bond followed by reductive elimination of the R-H.
The alkyl derivatives (PCsp3Pi-Pr)NiR (R ¼ Me, n-Bu) also react with PhX
(X ¼ Cl, Br, I) to give Ph–R and (PCsp3Pi-Pr)NiX [28]. This reaction can be carried
out under catalytic conditions to give the anticipated products of Corriu-Kumada
coupling with up to 80 catalytic turnovers; the homocoupling product Ph–Ph is also
144 D. Zargarian et al.
P
Ni Br
P
MeMgCl + PhCl Me-Ph + Ph-Ph
THF, reflux. 20 h
major minor
P= i-Pr2P
generated in minor quantities (Fig. 12). A number of mechanistic clues have been
obtained from the following experimental observations. First, NMR monitoring of
the catalytic runs has indicated that the alkyl derivative is the resting state in the
catalytic cycle, which implies that the coupling reaction catalyzed by this family of
pincer complexes does not involve Ni(0) species according to the conventionally
accepted Corriu-Kumada reaction mechanism. Second, the coupling efficacy
diminishes as i-Pr2P groups are replaced by t-Bu2P, underlining the importance of
steric factors, whereas the analogous PCsp2Pi-Pr system is virtually inactive,
highlighting the importance of electron density on the Ni center (vide infra).
Moreover, the observation that the homocoupling product Ph–Ph does not form
when (PCPi-Pr)NiPh is allowed to react with PhCl implies that the side reaction
leading to homocoupling likely proceeds via an outer-sphere (electron-transfer)
mechanism.
The charge neutral (PCsp3PR)NiBr complexes can be converted into different
cationic adducts. Thus, reacting the bromo precursors with MBPh4 (M ¼ Na, Ag)
in the presence of nitriles generates [(PCsp3PR)Ni(NCR0 )][BPh4] (R0 ¼ Me,
CH¼CH2) [41, 45]. Comparison of the n(CN) values in free acetonitrile and
[(PCsp3Pt-Bu)Ni(NCMe)][BPh4] (2,254 vs. 2,270 cm1) indicates some degree of
activation arising from the effective N ! Ni s-donation, whereas the corre-
sponding values for free and coordinated acrylonitrile (2,232 and 2,231 cm1,
respectively) imply much less activation of acrylonitrile. The n(CN) values in
the acetonitrile adducts featuring PCsp3Pi-Pr (2,274 cm1) and PCsp2Pi-Pr
(2,282 cm1) indicate that the latter ligand is a weaker donor in comparison to its
PCsp3P analogues, thus corroborating the redox data (vide supra). This conclusion
is also consistent with the observation that the [(PCsp2Pi-Pr)Ni]+ moiety better
activates acrylonitrile toward Michael-type hydroamination in comparison to its
PCsp3PR counterparts [45]. Available experimental evidence indicates that the Ni
center in these cationic pincer complexes acts like a Lewis acid to activate the C¼C
double bond of kN-acrylonitrile toward nucleophiles. Consistent with this postulate,
reacting aniline with [(PCsp3Pt-Bu)Ni(NCMe)]+ produced [(PCsp3Pt-Bu)Ni
(NCCH2CH2N(Ph)H)]+, which was isolated and fully characterized [45].
An interesting complex was obtained from the reaction of (PCsp3Pi-Pr)NiBr with
AgBF4. Even though the solid state structure of the product could not be deter-
mined, comparison of its spectral data to those for similar M-F-BF3 compounds has
allowed a fairly confident identification as (PCsp3Pi-Pr)Ni(BF4) [44]; the analogous
PCsp2P complex was reported by Peruzzini’s group very recently (vide supra).
Facile displacement of BF4 from (PCsp3Pi-Pr)Ni(BF4) has allowed the preparation
ECE-Type Pincer Complexes of Nickel 145
BF4
P L P L= OH2 P
Ni BF4 Ni L Ni OH
P P KN(SiMe 3) 2 P
P= i-Pr2P L= NCMe, OH2 , H 2N(i-Pr), CO
X
P FeX3 P
Ni X Ni X P= i-Pr 2P; X= Cl, Br
P CH2Cl2 P
3 NCN Complexes
As mentioned earlier, the NCN complexes of nickel were introduced shortly after
the first (PCP)Ni complexes, but the chemistry of NCN complexes experienced a
much faster growth owing, primarily, to their outstanding properties as catalysts,
146 D. Zargarian et al.
N
N
N N (THF)2 NiBr 2 D N N
N N Toluene Br
Ni N
Base
X N Ni N
N
r.t., 30 min Br Br
van Koten and his coworkers have played a pioneering role in the development of
(NCN)Ni complexes. This group reported in the early 1980s the synthesis of (NCN)
Ni(II) compounds and demonstrated their oxidation to Ni(III) species using mild
oxidants [48, 49]. Unlike their PCP counterparts that can feature either sp2 or sp3
carbon centers at the central position of the ligand, all known NCN complexes of
nickel feature sp2 carbon centers only, most being of the type 1,3-(CH2NR2)C6R0 3.
Another important difference between PCP and NCN ligands is that the latter do not
undergo nickellation readily and must, therefore, be introduced via different routes.
Moreover, when NCN ligands do undergo C–H metallation, with Pd precursors for
instance, the orthometallation often occurs at sites other than the central carbon (C-2)
of the ligand. van Koten et al. have proposed that the resistance of NCN ligands to
C–H nickellation is due to weak Ni–N bonds that hinder the prior chelation of the
metal center by the amine moieties [50]. On the other hand, it has been shown at
least in one case that C–H nickellation does not ensue even when the nickel center is
chelated (Fig. 15) [51]. One possible reason why C–H nickellation does not occur in
ECE-Type Pincer Complexes of Nickel 147
(PPh3 )AuCl Me 2N
NMe 2 Et2 O + (PPh 3) 2NiCl2 NMe 2
-30 °C to rt Toluene, r.t.
Li Au PPh 3 Ni Cl
- LiCl - (PPh 3)AuCl, - 2 PPh 3
NMe 2 NMe 2
Me 2N
this system is the weak ligand field of amine donors that leads to a tetrahedral
coordination as opposed to a square planar intermediate required for metallation.
Preparation of the very first (NCN)Ni complex was achieved via the oxidative
addition of 1,3-(CH2NMe2)C6H3Br to Ni(COD)2 (Fig. 16) [48, 49]. Subsequent
metathetic reactions using different salts (AgX, NaX or KX, where X ¼ Cl [43], I,
BF4, NO2, N3, NO3, OH, O2CH, O2CMe, O2CPh, O3SCF3) led to charge-neutral
derivatives (NCNMe)NiX. The acetate and formate derivatives were more easily
prepared with the cationic aquo adduct [(NCNMe)Ni(OH2)][BF4]. Interestingly, the
normally labile formate ligand was found to bind strongly to Ni in (NCNMe)Ni
(OCHO), which was characterized by X-ray diffraction studies. Indeed, this com-
pound proved more stable than its platinum analogue, remaining unaltered in
refluxing benzene. (NCN)Ni complexes, in general, are thermally stable and can
be sublimed. Curiously, given the superior electron donating ability of NCN
ligands, generation of pure samples of cationic species was reported to be some-
what difficult as these compounds were found to be air-sensitive. Later reports
confirmed the difficulty in isolating cationic (NCN)Ni adducts, but it was shown
that the problem can be resolved in some cases by altering reaction conditions and/
or using appropriate counter anions [52, 53].
An alternative to the oxidative addition route for preparing (NCN)Ni complexes
is the metathesis of a lithiated ligand with a Ni(II) precursor. This approach has
been used for the synthesis of many derivatives, including those used in the
manufacture of carbosilane-based dendrimers (vide infra). A third method,
introduced in 2002 by van Koten’s group, consisted of an elegant strategy based
148 D. Zargarian et al.
X'
N
MX'
X Ni X'
N CuX2 N N
AgOSO2 CF 3
Ni X Ni X
S
N or 1/2 X2 N or AgBF4 C
N
X= Cl, Br, I M= Li, Na NH4 NCS N
X'= NO2, NO3 Ni L
L= OH2, pyridine N
N
C
S
R1 H CCl4
Cl
CCl3
R2 H
R1 2
R
van Koten et al. also showed that the dihalo Ni(III) complexes discussed above can
be converted into various pseudo-halogen derivatives [56]. Interestingly, while Ni(III)
species bearing NO2 and NO3 gave the expected pentacoordinate complexes, the SCN
derivative turned out to be the 19 electron, hexacoordinated Ni(III) species shown
in Fig. 18. The solid state structure of this unusual complex showed longer than
expected Ni–NNCN bond distances. Taken together with ESR data, it was proposed
that the unpaired electron in this paramagnetic octahedral species resides in the dx2-y2
orbital due to a rare tetragonal contraction along the z-axis.
Kozhanov et al. have studied the structures and EPR spectra of (NCNR)Ni(III)
systems (R ¼ Me or piperidinyl) featuring a bidentate o-semiquinone spin-label
ligand [57]. Interestingly, they showed that the nature of the N-substituent
determines whether the unpaired electron will reside on the metal, which results
in a Ni(III) species, or on the semiquinone ligand, which gives a Ni(II) species. This
group has also investigated a mixed-halogen version of the first (NCN)NiX2
complexes reported by van Koten et al. Solution EPR studies of (NCN)Ni(Br)Cl
indicated that it exists as two isomers differing in the positions of Br and Cl (apical
or basal); this was confirmed by comparison to the spectra of independently
prepared homohalogen species (NCN)NiCl2 and (NCN)NiBr2 [58]. Interestingly,
X-ray diffraction analysis of (NCN)Ni(Br)Cl showed that the only isomer in the
solid state was the one with apical Br.
(NCN)Ni complexes have been shown to be active catalysts for the addition of
polyhalogenoalkanes to olefins, commonly referred to as the Kharasch addition
reaction or atom-transfer radical-addition (ATRA, Fig. 19). This reaction is of great
importance since it is atom efficient, creates a new C–C bond and introduces
halogen substituents which are useful for further chemical transformations. van
Koten et al. [59, 60] have demonstrated that the catalytic activities of (NCN)Ni
complexes are comparable to those of the best catalysts known for this transforma-
tion, such as RuCl2(PPh3)3 [61] and Pd(OAc)2/PPh3 [62]. For instance, (NCN)NiCl
(0.05 mol %) promotes the regioselective addition of CCl4 to methylmethacrylate,
at 25 C and after 72 h, with TON ~ 1,700 (CCl4:alkene, ~5.6:1). With a higher
catalyst loading (~0.8 %), (NCN)NiCl is active even at 0 C, whereas RuCl2(PPh3)3
is inactive below 40 C [61]. The favorable electronic and steric properties of NCN
150 D. Zargarian et al.
N CCl4 N Cl
Ni Cl Ni CCl2
N N Cl
Cl
CCl3
R1
R2
Cl Cl [CCl3 ]
R1 CCl3 N N
Ni Cl Ni Cl
R2 N N
R1
R2
ligands are highlighted by the fact that NiX2(PPh3)2 has a very limited activity for
promoting this reaction.
Detailed mechanistic studies have been performed and the main features of the
catalytic cycle have been identified (Fig. 20) [59, 60, 63]. The mechanism follows
a radical pathway involving the persistent radical pair species [(NCN)NiCl2]
[CCl3]. Consistent with the proposed mechanism, no induction of chirality is
noted in the Kharasch addition product when precursor complexes bearing chiral
ligands are used [64]. One deactivation pathway appears to involve the slow but
irreversible consumption of [CCl3], which leads to the formation of inactive
(NCN)NiCl2; such trivalent species are commonly found at the end of a catalytic
reaction.
An important factor to consider for the Kharasch addition reactions catalyzed by
(NCN)NiX is that the haloalkane (e.g., CCl4) and the olefin substrate (e.g., MMA)
must be used in approximately equimolar ratios in order to avoid an atom-transfer
radical polymerization (ATRP); this is the predominant reaction observed when
a large MMA:CCl4 ratio is used. Thus, it has been shown that (NCN)NiBr can
promote the ATRP of MMA and n-butyl methacrylate (n-BuMA) at temperatures
lower than 100 C [65]. The final polymers were found to have very high mole-
cular weights (~105 g/mol) and very narrow polydispersities (Mw/Mn < 1.3).
Block copolymerization was also successfully achieved between MMA and
n-butyl methacrylate. It is worth noting that since these NCN complexes are stable
to water, they can be used for aqueous suspension polymerization reactions.
Preliminary results show that monodisperse PMMA can be obtained when the
polymerization reaction is performed in aqueous media: Mn/Mw ¼ 1.7,
Mn ¼ 60,000 g/mol compared to Mn/Mw ¼ 6.5, Mn > 290,000 g/mol without
catalyst.
van Koten et al. have also demonstrated that active catalysts for the Kharasch
addition can be prepared by anchoring NCN pincer complexes at the periphery of
monodisperse, tree-like macromolecules commonly referred to as dendrimers [66].
A great advantage of using dendrimer-based catalysts is that they can be retained
ECE-Type Pincer Complexes of Nickel 151
O
O NH NH
HN O NH Si
O O O
O
O O NH
Si O O Si Si Si
Si NH
NH
Si O
O Si
NH NH
Si Si O O NH
O O
O
O
O O O NH
NMe2
HN O HN NH = Ni Cl
O NMe2
inside a membrane reactor during the catalytic reaction, allowing ready separation
of the catalysts from the reaction mixtures and their recycling. The feasibility of this
concept was first demonstrated with carbosilane dendrimers linked to NC(Br)N
ligand moities via carbamate units (Fig. 21).
Dendrimers bearing four and twelve catalyst end-groups were prepared in one
step via the oxidative addition of C-Br bonds to Ni(PPh3)4. Other dendrimer-based
materials have since appeared, including an amino acid-based dendrimer featuring
four (NCN)NiBr end-groups linked via urea units [67], and carbosilane dendrimers
bearing 4, 12, and 36 (NCN)NiBr end units (Fig. 21) [68]. The latter dendrimers
were assembled via the lithiation of the NC(Br)N end-groups and transmetallation
with NiCl2(PEt3)2 (vide supra). Other systems based on silica particles or polysiloxane
polymers have also been introduced [69, 70]. These metallodendrimers have been
shown to be active catalysts for the Kharasch addition reaction of CCl4 to MMA, but
comparison of reactivities has shown that dendrimers decorated with four (NCN)NiBr
units display lower turnover frequencies per nickel site compared to the corresponding
monometallic species; moreover, these macromolecular catalysts deactivate more
rapidly. van Koten et al. propose that this deactivation is due to the close proximity
of the Ni(II) units at the dendrimer periphery that accelerates the irreversible
formation of inactive Ni(III) species [68].
New families of (NCN)Ni complexes have been introduced over the past few years
and shown to promote catalytic reactions other than radical additions. For instance,
Richards et al. have reported the first bisoxazoline-based pincer complexes (known
as phebox, Fig. 22) and shown that they can act like Lewis acid catalysts [52].
Iodide abstraction using Ag(OSO2CF3) (in acetone over 27 h) led to a poorly
characterized product that could, nonetheless, promote the Michael addition of
152 D. Zargarian et al.
O O O
N Ni N CN
EtO
O O R R' Br R' R
CN +
EtO
Ag(OSO 2CF3 ) / Base O O
Fig. 22 Michael addition promoted by the first phebox pincer complex of nickel
R R R
O R' O R' O R'
N N N
PEt3
1. n-BuLi , -78 °C to r.t.
Br Ni Br + Ni Br
2. (PEt3)2 NiBr 2 , r.t.
N N Et3P N
O R' O R' O R'
R R R
O O
N Ni N
I N O
O C
5% OBu
+ OBu
Na2 CO3 , DMF, reflux
24-48 h TON= 5-16
R1 R1
R1
R2 R2 R2 R2
R2 R2
ClO4
O O O O
Ni(COD)2 O O
AgClO 4
N X N N Ni N
Toluene, rt N Ni N
CH 2Cl2
R3 R3 R3 R3
X R3 R3
OH 2
R = H, t-Bu, OMe
1 2
R = H, OMe
R3 = i-Pr, Ph, Bn X = Br, I
R2 R2 R2 R2
R1 R1 R1 R1
Ni(COD)2
N Br N N Ni N
THF
Br
R1 R1 R1 R1
1 2 1 2
R =R =Me; R = Et, R = H 68-72%
induction period in the Heck coupling reaction prompted these authors to suggest
that the cationic adduct is only a pre-catalyst for this reaction.
Bugarin and Connell have reported the preparation of numerous neutral and
cationic pincer complexes bearing chiral phebox ligands (Fig. 25) [72]. These
complexes should be ideal candidates for establishing structure/activity relationships,
but no study has been reported yet on their catalytic activities. Structural analyses
carried out on four of these complexes showed that the presence of an electron-
donating group such as t-Bu on the ligand resulted in elongation of the Ni–X bond,
presumably because the more electron-rich aryl ring exerts a greater trans influence.
The relative Lewis acidity of the cationic aquo adducts was evaluated by studying
their ligand exchange reactions in the presence of a sub-stoichiometric quantity of
acetonitrile (0.9 equiv.). Measuring the downfield shift of the CH3CN–Ni signal
compared to free acetonitrile, and assuming that this shift would be proportional to
154 D. Zargarian et al.
N N N N
N Ni N N Ni N
Br Br
R2 N R1 R2 N R1 R2 N R1 [BF4]
N N N
NiCl2 / NEt 3 AgBF4
H Ni Cl Ni NCMe
Toluene, reflux CH2 Cl2 / MeCN
40-48 h r.t., 12 h
N N N
2 N R1 R2 N R1 R2 N R1
R
the Lewis acidity of the (phebox)Ni+ fragment, a decrease in Lewis acidity was noted
as more electron-donating substituents were introduced on the phebox ligand.
New (NCN)Ni complexes featuring imine donor moieties have been prepared
by the groups of van Koten [71] and Park [73] (Fig. 26). As was the case for the
above-discussed phebox systems, theoretical calculations have suggested that,
unlike their bis(amine) analogues, these bis(imine)phenyl ligands are not suitable
for stabilizing trivalent species. The bis(ketimine)phenyl complex prepared by
Park et al. was found to be inactive for the polymerization of ethylene, giving
only small amounts of oligomers even with a high pressure of ethylene gas
(200 psi) and in the presence of large excess of methylaluminoxane (MAO,
1,000 equiv.; 3 h, 60 C).
A very recent report by Valderrama et al. describes new NCN pincer complexes
based on bis(azolylmethyl)phenyl ligands (Fig. 27) [74]. The charge-neutral
bromides were prepared via the oxidative addition of the brominated ligands to
Ni(COD)2, but attempts at isolating cationic adducts failed. Even though it was
found to be less active than its Pd counterpart for polymerization of ethylene, the
Ni-based bis(indazolyl) complex can produce under fairly mild conditions (60 C,
3.5 bar) high molecular weight polyethylene of relatively narrow polydispersities
(Mw ~ 119,000–200,000 g/mol; Mw/Mn ~ 2.3–2.8). According to the mechanism
proposed for this reaction, the catalytically active species is generated by dissocia-
tion of one of the Ni–N bonds; the lower activities of the Ni complex is attributed to
the short and less labile Ni–N bonds relative to the Pd complexes.
Finally, it was demonstrated very recently that (NCN)Ni species can be prepared
via C–H nickellation: C2-symmetrical 1,3-bis(20 -imidazolyl)benzenes react with
anhydrous NiCl2 in refluxing toluene to give a variety of (NCNim)NiCl in 40–87 %
ECE-Type Pincer Complexes of Nickel 155
yields (Fig. 28) [75]. Preliminary studies have shown that these optically active
complexes fail to promote stereoselective transformations, but their facile synthesis
via direct C–H nickellation bodes well for further development of the chemistry of
this family of (NCNim)Ni complexes.
The first POCOP complex of nickel, (POCOPPh)NiCl, was introduced in 2006 by the
group of Morales-Morales [78]. Shortly thereafter, Pandarus et al. reported the halo
complexes (POCOPi-Pr)NiX (X ¼ Cl, Br, I) [79, 80]. The latter reports emphasized
the importance of the nickel precursor for the synthesis of POCOP complexes. Thus,
simple derivatives such as NiBr2Ln (L ¼ THF or MeCN; n ¼ 1.5 or higher,
depending on the conditions of preparation) proved to be superior to NiBr2, whereas
the bromo precursors gave cleaner reactions and higher yields than their
corresponding chloro and iodo counterparts. Other precursors such as Ni(OAc)2,
Ni(NO3)2, Ni(acac)2, etc. were also less effective although little effort has been
expended on optimizing the metallation reaction with these precursors [51, 79].
The presence of a base such as DMAP or NEt3 was also found to be beneficial for
the yield. The (POCOP)NiBr can thus be obtained in 80–95 % yields from the
ambient temperature reaction of NiBr2(NCMe)2 with POCHOP in the presence of
NEt3; more recent work has shown that 90% or better yields are possible routinely
and on multi-gram scale [81]. It should be emphasized, however, that bases affect
only the yields of the final complexes and are not essential for the C–H metallation
reaction. Indeed, Morales-Morales reports that (POCOP)NiCl can be prepared in
80 % yield without any added base [78]; it is not clear how the HCl generated in-situ
is neutralized or removed from the reaction medium. This latter point is important
for our understanding of the mechanism of the nickellation step (vide infra).
156 D. Zargarian et al.
O O
i-Pr 2 P Ni P(i-Pr)2
R= i-Pr OH 2
O O O O OTf
NC H 2O
R 2P Ni PR 2 R 2P Ni PR 2
N OTf R= Ph
OTf O O
OTf = OSO 2CF3 PPh 2
PPh 2
O O
R'OH CN H2 O OH 2 OTf
HNR'2 Ni
OTf H 2 O OH 2
O O
'
RO
CN Ph2 P Ph2 P
O O
O O
R 2P Ni PR 2
N
OTf
R 2' N
Cl NH2 H CN
O P N
OTf
CN H
Ni N C Me + Cl N NH 2
NEt3, 60 °C, 24 h
O P
Cl
1% 1-2%
H 73%
N
P= P(i -Pr 2) O P OTf
O
Ni N N
60 °C H
24 h O
O P
O O
Ph 2P Ni PPh 2
Cl
I + 1/2 RS-SR SR
Zn, DMF, 110 °C, 4 h
KOH K
O O (4 equiv) O O O O H
P Ni P P Ni P + P Ni O
DMF, 80 °C P
Cl PPh 2 OH
2h O
KOH K K
O O (excess) O O H O O H
P Ni P P Ni O + P Ni O
DMF, 80 °C P P
SAr 2h SAr OH
H
O O R O O O
P= i-Pr 2P P Ni P P Ni P
H O R
H2 PhSi
O R PhSiH3
O
[Ni]= (POCOPt-Bu)Ni H BCat = BH
MeOH O
O O
CO2 H BCat BCat
H 2O [Ni] H [Ni] O H H O
BCat [Ni] H
Me O
H BCat
CH 3
[Ni] O BCat
[Ni] O O
H BCat O
O [Ni] H [Ni] O
H H
H H BCat
BCat
O
BCat
(PhSiH3 ~ Ph2SiH2 > Et3SiH, (OSi(Me)H)n > > HSi(OEt)3), thus making possi-
ble a catalytic cycle for hydrosilylation of aldehydes (Fig. 33). Screening studies
showed that (POCOPi-Pr)NiH catalyzes hydrosilylation of a variety of aromatic and
aliphatic aldehydes with 300–450 catalytic turnovers; a,b-unsaturated aldehydes
gave products of 1,2-addition and isolated C¼C was not hydrosilylated.
Hydrosilylation of ketones gave generally lower yields, and the POCOPt-Bu ana-
logue was much less active. The inertness of (POCOPi-Pr)NiH toward PhSiH3 even
at elevated temperatures indicated that the hydrosilylation mechanism in this
system involves initial insertion of the carbonyl group.
The complexes (POCOPR)NiH also react with CO2 to generate a labile formate
derivative, which is in equilibrium with the starting hydride (Fig. 34) [85, 88].
Interestingly, excess catecholborane drives this equilibrium toward formaldehyde
and, eventually, methanol. This process is favored by bulky phosphinite moieties
(t-Bu > c-Pen and i-Pr). Experimental observations and computational studies
have helped uncover a complex catalytic cycle based on metathesis-type reactions
of the type LNi(R) + A-X ! LNi-X + R–A [93].
ECE-Type Pincer Complexes of Nickel 161
O P (MeCN) 2NiBr2 O P
P= i-Pr2 P Ni Br
O P DMAP, Toluene O P
reflux, 5 h, 93%
(THF)1.5NiCl2
X
Toluene, r.t., 1 h Toluene, ref lux
Base
O O
O P P P Cl
Cl Cl
Ni Ni Ni
O P Cl Cl
Cl P P
O O
X
Cl
O P CuX2 O P R , CCl4 CCl3
Ni X Ni X R
O P hexane/ O P acetonitrile
acetone 85 °C, 24 h
P= i-Pr2 P
H
N P P (C 6F5 )3 B N P
(dme)NiCl2 N
H Ni Cl Ni Cl
HN P NEt3, THF HN P Toluene HN P
r.t., 20 h r.t., 10 min
P= t -Bu2 P
78% 48%
The first, and so far only, authentic (PNCNP)Ni complexes featuring an anionic,
terdentate ligand is the complex [CH{(CH2)2NHP(t-Bu)2}2]NiCl reported very
recently by Gwynne and Stephan [97]. These authors showed that metallation of
PNCsp3HNPt-Bu is more facile with Pd than Ni: whereas this ligand undergoes
ECE-Type Pincer Complexes of Nickel 163
O NR2 P(i-Pr) 2
1. HNR 2 , NaBH4
OH MeOH, 0 °C O
H
2. i-Pr 2PCl, NEt3
THF, -5 to 0 °C
NR2 = NMe2 , NEt2 , 60 °C NiBr 2 (NCCH3 )x
3-4 h NEt3 /C6 H 6
N O
Br Br Br
R 2N Ni P(i-Pr)2 R2 N Ni P(i-Pr) 2
O O
Br2
metallation with PdI2 at r.t., the reaction with (dme)NiCl2 at r.t. and in the presence
of NEt3 gave a purple solid arising from the activation of the N–H bond instead
(Fig. 37). Subsequent reaction of this unusual species featuring a strained three-
membered P–Ni–N metallacycle (Ni–P–N angle ~ 58 ) with the strong Lewis acid
(C6F5)3B furnished the desired (PNCsp3NPt-Bu)NiCl in 48 % yield via a net transfer
of proton from the central CH2 moiety to the metallated N atom. The mechanistic
details of this transformation remain obscure, but DFT studies seem to suggest that
the C-metallated compound is more stable than the N-metallated analogue by ca.
10 kcal/mol. Structural characterization of (PNCsp3NPt-Bu)NiCl has revealed a
fairly large bite angle (P–Ni–P ~ 168 ); interestingly, the Ni–C and Ni–P distances
are longer than those observed in the analogous (POCsp3OPi-Pr)NiCl [80]. The
reactivities or redox properties of this new pincer compound have not been
reported.
The first (POCN)Ni complexes were introduced by Spasyuk et al. in 2009. These
ligands are accessible via a relatively simple two-step synthetic route and their
nickellation proceeds at 60 C over 3–4 h (Fig. 38) [98]. As was observed for the
preparation of PCP and POCOP complexes, the judicial choice of nickel precursor
and base is important for maximizing the yield of the desired pincer species. Most
examples of (i-PrPOCNR)NiBr examined to date are stable to ambient air, both in
the solid state and in solution. Moreover, solid samples of these compounds are
thermally stable above their melting points and can be sublimed under vacuum.
Solid state characterization shows a fairly planar structure, consistent with the
presence in the solution of a plane of symmetry incorporating the coordination
plane and the aromatic ring. Consistent with the weaker trans influence of an amine
moiety relative to a phosphinite donor, the Ni–P distances are shorter in POCN
systems relative to their POCOP analogues (2.11 vs. 2.15–2.16 Å), whereas the
Ni–N distances are longer in POCN complexes relative to their NCN analogues (ca.
2.05–2.07 vs. 1.97–1.99 Å). The Ni–C distances are similar in POCN and POCOP
complexes (ca. 1.88–1.90 Å), but much shorter in their NCN analogues (ca.
1.81–1.83 Å), presumably reflecting the tighter binding of the NCN ligand.
Another major difference between (POCOP)NiBr and (POCN)NiBr is that the
latter are easier to oxidize electrochemically and give access to isolable trivalent
species (Fig. 38), making these the only pincer-type aromatic ligands other than
NCN to allow isolation of trivalent species. Single-crystal X-ray diffraction studies
have revealed that (POCN)NiBr2 adopt structures similar to the above-discussed
(POCsp3OPi-Pr)NiBr2 and (PCsp3Pi-Pr)NiBr2 with elongated Ni–Brapical distances
(2.43–2.46 vs. 2.37 Å) [98]. That the unpaired electron resides in primarily Ni-
based molecular orbitals (a hybrid of dz2 and pz orbitals) was confirmed by EPR
spectra, which displayed a nearly axial g-tensor with strong hyperfine coupling to
the Br nucleus on the gzz component. In addition, a number of small, partially
resolved hyperfine splittings were observed due to coupling by the phosphorus (spin
1/2), nitrogen (spin 1), and/or in-plane Br nuclei (spin 3/2).
It is noteworthy that (POCN)NiBr2 are fairly robust both in the solid state and in
solution, and that thermal stability of these complexes appears to be greater in
systems bearing less bulky amine moieties. Thus, solid state samples of the
morpholinyl and NMe2 analogues can be heated up to 160 C without significant
decomposition, whereas the NEt2 derivative decomposes above 60–70 C; similarly,
the solutions of the latter display a t1/2 of ~20 min at 30 C, whereas the morpholinyl
and NMe2 analogues showed half-lives of 3–4 h at 70 C. The less bulky complexes
are also more active in the Kharasch addition of CCl4 to styrene [98].
Spasyuk et al. have also introduced a (POCN)NiBr complex featuring a second-
ary amine moiety that allows the preparation of new derivatives, including a rare
dimeric system that has shown interesting reactivities [99]. Deprotonation of the
N–H moiety of (i-PrPOCNH)NiBr results in formation of a dimeric species that
adopts an overall butterfly-like structure consisting of two T-shaped (POCN)Ni
halves that are rotated with respect to each other by about 70 C (Fig. 39). These
two halves are connected to each other by two Ni–N linkages and form a central
Ni2N2 core. The cyclobutane-like conformation of this Ni2N2 core places the
ECE-Type Pincer Complexes of Nickel 165
O O
Br 1. MeLi/ Toluene
P P
-78 °C, 30 min
(Bn)HN Ni P Ni Ni
O 2. 60 °C, 32 h N
Br N
O N O Bn Bn
P= i-Pr 2P
Br ROH CN
Br
BnN Ni P
O
RO
CN
Cl Cl Ph
O Ph
N Ni P N Ni P N
N X O
N
Ar Ar
P= PPh2
X= O, N
N-substituents syn to each other and the Ni centers within covalent bonding
distance. This dimeric species has proven to be an efficient catalyst for the
alcoholysis of acrylonitrile, giving the anti-Markovnikov (linear) product with up
to 2,000 catalytic turnovers; nonbulky alcohols possessing an acidic O–H moiety
showed the highest activities.
The dimeric species also displays interesting redox properties [100]. Cyclic
voltammetry measurements have shown that the dimer undergoes a reversible
one-electron oxidation, and DFT analyses have concluded that most of the spin
density in the putative radical cation is localized on one of the two Ni centers,
creating a mixed-valent species. Chemical oxidation of the dimer using NBS led to
the formation of divalent and trivalent monomeric complexes featuring a new
imine-type POCN ligand; the direct preparation and characterization of these new
species was undertaken as part of a study to investigate the mechanism of the
oxidation process. The solid state structures of these new POCN–imine complexes
are quite similar to those of their POCN–amine homologues, but the sp2-hybridized
nitrogen atom of the imine moiety forms somewhat shorter Ni–N bonds [100].
The first optically active POCN-type pincer complexes of nickel were reported
by Song, Gong, and coworkers in 2010 (Fig. 40) [101]. One ligand precursor
featuring an imidazolinyl moiety was prepared in four steps and subjected to a
166 D. Zargarian et al.
NR RN
N N
Ag N NR
(PPh 3)2 NiCl2 Cl
1/2 Ni NCMe
MeCN
r.t., overnight N NR
Ag (in the dark)
N N
NR RN R= Ph; 2,4,6-Me3 -C 6H 2
The first, and so far only, nickel complex featuring an anionic terdentate SCS-type
pincer ligand was reported by Gebink, van Koten, and coworkers [104]. The
complex (SCSMe)NiBr was prepared in 72 % yield as an air-stable yellow solid
by oxidative addition of SCBrSMe to Ni(COD)2 at 80 C. Interestingly, this
complex does not undergo reversible oxidation as do its NCN and PCP analogues,
presumably because the sulfur moieties are prone to oxidative decomposition. The
solid state structure of (SCSMe)NiBr has revealed that it adopts a rac conformation
with the two S-Me groups positioned on opposite sides of the coordination plane.
The Ni–C distance is similar to the corresponding distance in PCP systems (ca.
1.90 Å) and somewhat longer than that in NCN complexes (1.81–1.83 Å). Variable
temperature solution NMR studies have revealed a fluxional process involving ring
puckering inversion. The chemistry of (SCSMe)Ni complexes remains unexplored.
The first, and so far only, nickel complexes featuring an anionic terdentate ECE-
type pincer ligand based on NHC carbene donor moieties were reported by Chen’s
ECE-Type Pincer Complexes of Nickel 167
The literature survey presented in this chapter reveals that the chemistry of pincer-
type (ECE)Ni complexes is experiencing a resurgence that should lead to exciting
developments over the next decade. As was pointed out throughout the discussion
above, the family of NCN complexes has been at the forefront of this area of
organonickel chemistry for the past 3 decades. The relative maturity of the chemis-
try of (NCN)Ni complexes is undoubtedly owing to the pioneering studies and
sustained efforts of van Koten’s group, but the past few years have witnessed the
emergence on the scene of a number of new research groups that promise to expand
the frontiers of this area in new directions. A similar scenario is at play in other
families of (ECE)Ni complexes. For example, after being fairly dormant for nearly
2 decades, the chemistry of PCP complexes is being pursued by a growing number
of research groups that are re-examining the chemistry of complexes pioneered by
Shaw’s group, introducing new complexes based on new ligand frameworks and
exploring their reactivities. The related family of POCOP complexes has grown
even more rapidly since its introduction barely 5–6 years ago, and new catalytic
transformations are being developed based on these complexes. The chemistry of
recently introduced PNCNP, POCN, PNCN, SCS, and ĈCĈ complexes is less-
developed, but these compounds are poised to make major contributions to the
chemistry of pincer-type nickel complexes.
While it is generally true that predicting future developments in scientific research
is an exercise of questionable value, it is nevertheless interesting to try to identify the
likely direction of future developments in the area of pincer-type nickel chemistry.
168 D. Zargarian et al.
Regarding NCN complexes, for example, the reactivities of trivalent complexes will
likely be a fertile area of growth, as it has been over the past. An important
development would be the expansion of the radical chemistry promoted by open-
shell (NCN)Ni(III) species to different types of C–C coupling reactions, including
olefin oligomerization/polymerization chemistry and cyclization reactions. It is also
tempting to speculate that any development in this area should spill into the chemistry
of trivalent compounds featuring POCN, PCsp3P, and POCsp3OP ligands. Related
developments are also anticipated in the family of diamagnetic-at-Ni complexes
featuring unpaired electrons residing on an auxiliary ligand.
The very recently reported reactivities of (PCP)NiH and (POCOP)NiH
complexes augur well for significant future developments. Initial observations
indicate that insertion chemistry with unsaturated substrates such as CO2,
aldehydes, ketones, imines, nitriles, etc. should lead to interesting discoveries and
applications, whereas new reactivities in the area of C–H activation cannot be ruled
out. The related hydrocarbyl derivatives (PCP)NiR and (POCOP)NiR have shown
interesting C–C coupling reactivities with aryl and alkyl halides; studies aimed at
elucidating the mechanistic details of these reactions (e.g., establishing whether
these coupling reactions follow a constant-oxidation-state path or proceed via
fleeting Ni(IV) intermediates) should open the way for more efficient and sophisti-
cated applications. Similarly, developments in delineating the mechanistic features
of Michael addition reactions promoted by cationic complexes (e.g., [(NCN)NiL]+
or [(POCOP)NiL]+) and alcoholysis of olefins catalyzed by (POCOP)Ni(OR) or
{(mN-POCN)Ni}2 should lead to new reaction pathways and useful applications.
The above developments are fairly easy to anticipate on the basis of recent
observations, but it is harder to envisage new developments in areas that have seen
little or no activity. For instance, the above-discussed proposal by the Morales-
Morales group regarding the involvement of monovalent species generated in-situ
from (POCOP)NiX/Zn has the potential to open up a new horizon in the reactivities
of pincer-type nickel complexes. It remains to be seen, however, whether well-
defined monovalent species will be isolable and amenable to reactivity studies. An
even more intriguing possibility is the development of synthetic routes to tetrava-
lent species, which would promise exciting developments paralleling the more
developed chemistry of high oxidation state Pt and Pd complexes. Based on their
respective oxidation potentials, the best candidates for tetravalent species should be
complexes of NCN or PCsp3P pincer ligands.
The potential developments outlined above should make the chemistry of (ECE)
Ni pincer complexes an exciting field of research over the next decade.
Acknowledgments The authors wish to thank the Natural Sciences and Engineering Research
Council of Canada for financial support of our studies on pincer complexes of nickel. We
recognize gratefully all those collaborators who have helped us in our studies, including those
whose unpublished results are cited in this review, as well as those pioneers of pincer chemistry
whose discoveries have inspired our own work.
ECE-Type Pincer Complexes of Nickel 169
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Top Organomet Chem (2013) 40: 175–202
DOI: 10.1007/978-3-642-31081-2_6
# Springer-Verlag Berlin Heidelberg 2013
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
2 Result and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
2.1 Group 13: Ga, In, Tl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
2.2 Group 14: Ge, Sn, Pb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
2.3 Group 15: As, Sb, Bi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
3 Conclusions and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
1 Introduction
The chemistry of pincer ligands and their organometallic derivatives belongs for
more than 30 years to the most exciting and interesting areas of the chemical
research in the field of organometallic chemistry. Since the first utilization of
these ligands in late 1970s [1–3], the pincer chemistry has been developing to
very rich branch of chemistry and the topic results have been often reviewed [4–6].
The main afford in the field has been devoted to the chemistry of transition metals
and prepared compounds were found wide utilization in catalysis, material
sciences, and various types of physical applications as well demonstrated by
other chapter of this thematic issue of Topics on Organometallic Chemistry. On
the contrary, related chemistry of main groups stood a bit in the background,
although, for example, organotin(IV) compounds were studied directly at beginning
of the pincer story in 1978 [7]. The situation has recently changed, when Cowley
and others have started to prepare wide range of main group metal compounds and
later on Jurkschat et al. reported syntheses of the first OCO pincer type ligand and
its utilization in organotin and organosilicon chemistry. Since that time it seems that
pincer chemistry of main group elements starts to retrieve and several noteworthy
achievements were obtained.
This chapter is focused on recent progress in the pincer chemistry of heavier
group 13–15 elements, i.e., Ga, In Tl from the group 13, Ge, Sn, Pb—especially low
valent compound with formal oxidation state +II or +I from the group 14, and As,
Sb, Bi from the group 15. Only the classical pincer ligands, which constitute from
disubstituted phenyl rings, containing nitrogen or oxygen donor atoms are consid-
ered (Fig. 1). Related ligands containing other donor atoms such as P, S, etc. and
ligands, which are called pincer ligands, but differ significantly from the former
classical ligands by their structures are not covered and are beyond the scope of this
chapter.
The result and discussion section is organized in such a way that the chemistry is
discussed according to the central atom used and the authors try to encompass all
results till spring 2011 with one exception of compounds containing tetravalent
group 14 elements. This pincer chemistry is rather rich and has been already
reviewed [8]. Thus, the part dealing with group 14 elements is devoted mainly to
low valent compounds and their reactivity.
compounds derivatives of LO1,2 were prepared and characterized, but these are
beyond scope of this text [9, 10].
The starting chloro-complexes of gallium and indium LN1GaCl2 a LN1InCl2 are
easily prepared by conversion of starting lithium compound with gallium(III) and
indium(III) chloride, respectively. The mixed chloro-alkyl-compounds may be
obtained via the same reaction pathway with respective alkyl derivatives [11].
The chemistry of LN1GaCl2 a LN1InCl2 has been further studied. Thus, the reaction
of LN1GaCl2 with Li[GaH4] produces expected gallane LN1GaH2, which display
significant stability thanks to presence of the pincer ligand LN1. Using of Li[GaH4]
as a reagent is not casual, because using of aluminum analogue Li[AlH4] led to
transmetalation under formation of LN1AlH2. Analogously, treatment of LN1InCl2
with Li[GaH4] gave only compound LN1GaH2. Reactivity of the gallane LN1GaH2
with various reagents including Et2Zn and acids was further investigated according
to the Scheme 1 [12]. Furthermore reaction of LN1GaCl2 with sodium azide yielded
LN1Ga(N3)2, which was studied as a potential precursor of production of GaN [13].
Reaction of LN1GaCl2 and LN1InCl2 with Na[Co(CO)4] led to formation of
interesting bimetallic compounds with two Ga–Co and In–Co bonds [14]. Similarly
interesting is preparation of four membered Ga2P2 ring system, in which the gallium
atoms are stabilized by the pincer ligand LN1 [15]. Regarding the indium chemistry,
compound 9,10-dihydro-9,10-bis[2,6-bis-((dimethylamino)methyl)phenyl]-9,10-
diindaanthracene with the first six-membered diindacycle In2C4 was prepared by
the reaction of LN1InCl2 with o-phenylmagnesium, characterized in the solid state
and indium atoms are again supported by the ligand LN1 [16]. Finally, partial
reduction of LN1InCl2 allowed isolation of the compound LN1In(Cl)-In(Cl)LN1,
which contains In–In bond and indium atoms have unusual oxidation state II+ [17].
178 R. Jambor and L. Dostál
As mentioned earlier, the chemistry of 14 group elements in the oxidation state +IV
is intensively studied and behind several articles, there are also reviews dealing
with this topic [8, 19–22]. The organotin(IV) compounds containing NCN-
chelating ligand LN1 were most probably the first main group metal complexes
bearing pincer type ligand and they are investigated so far. While group of Corriu
used the same ligand in the organosilicon(IV) chemistry [23–30], examples of
NCN-ligand containing organogermanium(IV) complexes are practically unknown
[31]. Furthermore, the influence of Y,C,Y-pincer ligands on the reactivity and
coordination arrangement of central tin atom in organotin(IV) compounds has
been shown. For these reasons, the following paragraphs will be mainly focused
on low valent compounds of 14 group heavier elements containing YCY-ligands.
There are several methods used for the preparation of low valent compounds of
14 group elements providing hundreds of compounds. Most of these compounds
are, however, so-called homoleptic metallylenes of type R2M with different
The Chemistry of Pincer Complexes of 13–15 Main Group Elements 179
NR2 NR2
Li + GeCl 2.C4 H8 O 2 Ge Cl
NR 2 NR2
LN1 GeCl
R = Et, iPr
N1
L Ge CSiMe3
t H
BuO
(1)
t
N1
+ BuOH N1
L GeCSiMe3 L Ge=CHSiMe3
(2) t
BuO
(3)
N1
L Ge CSiMe3 + t BuOH
t
BuO H
+ tBuOH
L Ge(Ot Bu)2CH2SiMe3
N1 N1
L Ge CSiMe3
from hydrolytic cleavage of Si–N bond along the formation of Me3SiOH leaving
thus Ge–N bond unaffected. In the second step, acidic silanol can attack the Ge–N
bond producing [LN1Ge(OSiMe3)]W(CO)5 (Scheme 4).
NEt2
W(CO)5
Ge + (Me3Si)2NH
OH
NEt 2 NEt2 NEt2
W(CO)5
H2O
Ge N(SiMe3)2 + W(CO)5*THF Ge
N(SiMe3)2
NEt 2 NEt2 NEt2
W(CO)5
Ge + Me3SiOH
NHSiMe3
NEt2
NEt2
W(CO)5
Ge + Me3SiNH2
OSiMe3
NEt2
O2 O2
air moisture O2 O2
2 (L )Li + SnCl2 (L )2Sn (L )2(OH)SnOSn(OH)(L )2
H3C CH3
Si CH3
NMe2 O Me2N
O
Sn Sn
O
NMe2 O NMe2
H3C Si
H3C CH3
N1
THF N1 N1
2 L SnCl + 2 K[sec-Bu3BH] L SnSnL
- KCl, sec-Bu3B, -H2
N1 S N1
L Sn Sn L
S
S S
S S
S8 S
N1 N1 E N1 E N1
L Sn Sn L L Sn Sn L
E = S, Se
Se
Se
N1 N1
L Sn Sn L
Se Se
The heteroleptic stannylenes LPOSnX (X ¼ Cl, Br) were used as precursors for
preparation of the heteroleptic stannylenes LPOSnX (X ¼ CH(SiMe3)2, SiPh3,
SnPh3, and SnMe3) as a result of the substitution reactions. The oxidation of the
former stannylenes provided the tetravalent monorganotin derivatives {LPOSnCl
(m-S)}2 and LPOSnBr3 and the diorganotin cation {LPO(Ph3C)(Cl)Sn}+[PF6]
(Scheme 8) [70].
As the oxidation state of the tin atom is +II and there are only two covalent bonds
presented in the stannylenes, these compounds can be an alternative to the carbene.
In these functional substituted organostannylenes, the Lewis base character of the
The Chemistry of Pincer Complexes of 13–15 Main Group Elements 183
EtO
EtO P O
t
Bu Sn
SPh
EtO
EtO EtO P O
EtO P O OEt
EtO P O EtO
O P OEt
t
t NaSPh Bu Sn S
Bu Sn
S t
R - NaCl Sn Bu
LiR
EtO P O
EtO P O
- LiCl 1/8 S8
EtO EtO O P OEt
EtO
EtO P O OEt
R = CH(SiMe3)2, SiPh3
R = SnPh3, SnMe3 t
Bu Sn
Cl
+ -
O Ph3C PF6
M(CO)5*THF EtO P
EtO EtO EtO
EtO P O EtO P O
-
t
1/2 Fe2(CO)9 t + Cl PF6
M(CO) 5 Sn
Bu Sn Bu
- CO CPh3
Cl
EtO O
EtO P O EtO P
EtO EtO P O EtO
M = W, Cr t Fe(CO) 4
Bu Sn
Cl
EtO P O
EtO
Y Y
LN1; Y = NMe2
[M]SnCl2 [M] LO1; Y = OMe
Li Sn LO2; Y = OtBu
- LiCl
Cl LPO; Y = PO(OEt)2
Y Y [M] = (CO)5Cr, (CO)5Mo, (CO)5W
O
N Cr Cr
Sn
Sn
N O
W Sn
O(w) O(w) O
O
CO
R R1 Cl CO Cl CO
Pd Ru Rh
Ru Cl CO
LN1SnCl Cl Cl CO
LN1SnCl LN1SnCl LN1SnCl
Cl
R = R1 = H
R = Me, R1 = iPr
result of the simultaneous replacement of CH3CN by the LN1SnCl and chloride ion
transfer from another molar equivalent of stannylene. As all prepared complexes of
LN1SnCl contain both Sn–Cl and M–Cl bonds, the question concerning the reactiv-
ity of these functionalities towards nucleophiles came into mind. The
organostannylene palladium-based complexes were studied in this field unsuccess-
fully and the only positive result was obtained when the organostannylene complex
[LN1SnCl][2-(Me2NCH2)C6H4]PdCl that contains both a NCN- and a CN-
coordinating ligand was treated with silver acetate (AgOAc). This reaction gave,
under exclusive Sn–Cl substitution, the monoacetate-substituted complex
[LN1SnOAc][2-(Me2NCH2)C6H4]PdCl [78].
For further reactivity studies, kinetically more stable complex cis-
[LN1SnCl]2PtCl2 was chosen. Treatment of cis-[LN1SnCl]2PtCl2 with four
equivalents of NaI provided trans-[LN1SnI]2PtI2 [76]. Both platinum complexes
undergo reaction with three equivalents of NaSPy providing interesting complexes
[LN1Sn]+[PtX(SPy)2] (X ¼ Cl, I), where stannylidenium (LN1Sn)+coordinates Pt
center (Fig. 4) [66].
From the structural point of view, the Sn–Pt interaction could be interpreted as a
Sn ! Pt or Sn Pt interaction or a covalent bond in these complexes. DFT
calculations of [LN1Sn]+[PtX(SPy)2] (X ¼ Cl, I) were performed and the NBO
analysis revealed no lone pair at the tin atom and the natural charge of Sn atom is
The Chemistry of Pincer Complexes of 13–15 Main Group Elements 187
+1.709, while at the Pt atom is 0.486. These observations were rationalized with
the lone electron pair of Sn(II) atom being shared by both atoms and consumed for
the formation of tin–platinum bond. The NBO analysis showed that the nature of
the Sn–Pt bond is mediated by sp-hybridized orbitals on the tin atom (Fig. 5). The
bonding situation was also described within a Sn(IV) Pt(0) formalism [66].
The ability of the heteroleptic stannylenes containing YCY-chelating ligands to
complex late transition metals is probably the function of the strength of Y ! Sn
interaction. When stannylenes LO1,2SnCl were treated with late transition metal
complexes, only the decomposition reactions were observed. However, when
another oxygen atom containing stannylene LPOSnCl having stronger O ! Sn
coordinations was applied for binding of transition metals, stable Sn–TM
complexes were prepared. Treatment of LPOSnCl with PdCl2, PdI2, and PtCl2
yielded cis-[LPOSnCl]2MX2 complexes, similarly to LN1SnCl [76]. After reaction
of LPOSnCl with dimeric Ru(II) complex, stable complex [LPOSnCl]Ru(C6H6)Cl2
was isolated (Scheme 14) [79].
188 R. Jambor and L. Dostál
Scheme 14 Complexes of
LPOSnCl X
heteroleptic stannylene
LPOSnCl M Ru
LPOSnCl X Cl PO
Cl L SnCl
M = Pd, Pt X = Cl, I
Scheme 15 Cyclization of
organoarsenic(III) and
organoantimony(III) OCO
chelated compounds
The chemistry of the group 15 elements was not studied so often in the past, but
during the last few years this field has been opened again by our group and groups
of Prof. Breunig, Prof. Silvestru, and more recently by Prof. Evans.
Organoarsenic(III) compounds were prepared by simple reaction of
organolithium compounds with AsCl3 of pincer ligands LN1 and LNO2 and targeted
The Chemistry of Pincer Complexes of 13–15 Main Group Elements 189
i
PrO EtO
i
PrO P O EtO P O
t
PbCl2 t
Bu Li Bu Pb
- LiCl Cl
EtO P O
iPrO P O
iPrO EtO
Scheme 17 Preparation of antimony fluorides containing pincer type ligands and an example of
molecular structure
Fig. 6 Molecular structures of bismuth and antimony cations stabilized by pincer ligands, the
structures of counter-anions [CB11H12] are omitted for clarity and each central atom carries +I
charge
these compounds form infinite chains in the solid state via bridging by oxo-anions
or dimeric structure in the case of the nitrate LN1Bi(NO3)2 [96]. Evans et al.
enriched this class of compounds by preparation of bismuth bulky phenolates
containing ligand LN1, which undergo an extremely interesting CH activation,
and formation of NCN chelated organobismuth compound with a monodentate
carbon-bound oxyaryl dianion (C6H2-t-Bu2-3,5-O-4)2 [97].
Not only oxides are stabilized by pincer type ligands, but also heavier
chalcogenides are accessible. Thus, the reactions of chlorides LO1,2MCl2 (M ¼ Sb
or Bi) with an excess of sodium sulfide gave corresponding sulfides [LO1,2MS]2,
which are dimeric both in the solid state and in solution with central M2S2 four-
membered central ring. The pincer ligands may be placed on this ring in a cis or
trans fashion and both isomers were detected in solution and in the solid state; the
central M2S2 ring is planar in the trans isomer but strongly puckered in the cis one
[98]. Analogous NCN chelated compounds [LN1MS]2 (M ¼ Sb or Bi) are also
dimers in the solid state according to X-ray crystallography studies, but more
importantly they dissociate in solution into monomeric compounds with terminal
M–S bonds. Presence of these unprecedented monomeric derivatives was
established by trapping experiments with sulfur and carbon disulfide (Scheme 19)
[99, 100]. Especially isolation of dinuclear bispentasulfides is noteworthy, because
they represent new structural type among organometallic polysulfides in general.
Reaction of low valent organoantimony(I) compound [LN1Sb]4 (see next
The Chemistry of Pincer Complexes of 13–15 Main Group Elements 193
Fig. 7 Description of terminal Sb–E (E ¼ Se, Te) bonds based on theoretical considerations
Scheme 20 Preparation and reactivity of low valent NCN chelated organobismuth compound
ligand LN2SbCl2 gave besides expected monomeric selenide LN2SbSe also unprec-
edented monomeric sulfide LN2SbS with the first terminal Sb–S bond (Dostál L
et al., unpublished results). Heavier chalcogenides (Se, Te) of organobismuth pincer
compounds remain still elusive and represent synthetic challenge for future
research.
Besides wide utilization of pincer ligands in the field of organoantimony(III) and
organobismuth(III) compounds, it has been recently demonstrated that these
ligands are able to stabilize low valent organoantimony and organobismuth
compounds, which display interesting reactivity.
The reduction of (LN1)2BiCl with magnesium in THF produced compound
(L )2BiBi(LN1)2 with single bond between two bismuth atoms. This compound
N1
LN2 and the same synthetic protocol, i.e., reduction of starting chlorides with K-
selectride allowed isolation of unique deep blue compounds LN2M (M ¼ Sb or Bi)
[104]. These compounds contain the central atoms in formal oxidation state +I and
there are no additional intermolecular contacts between the central atoms, which
makes them exclusively monomeric, which is unprecedented in the group 15
chemistry. This is again result of excellent properties of the NCN pincer ligand,
which blocks empty p-type orbital of the central atom by interaction with nitrogen
donor atoms and at once shields the full p-type orbital of the central atoms by its
sterical demanding flanking aryls on the ligand’s arms. As shown by theoretical
calculations presence of the pincer type ligand is crucial for stabilization of these
compounds LN2M (M ¼ Sb or Bi). This fact was further supported by experiment,
which showed that using only NC single-armed chelating ligand allowed isolation
of low valent antimony compounds, which are tetrameric [105] (Fig. 8).
196 R. Jambor and L. Dostál
The pincer chemistry of main group elements has recently been enriched signifi-
cantly and several very interesting results were discovered; nevertheless, it is felt
that this chemistry in comparison to the transition metals analogues is still in its
infancy. The pincer type ligands are able to stabilize not only routine compounds
but also rather unstable and reactive species even with low valent metal atoms. In
such a way they may form an attractive alternative to sterically demanding ligands
used by Power and others for stabilization of such organometallic species. As it is
known, compounds with low valent metal centers and(or) with metal–metal bonds
display an extremely interesting reactivity [106], similar reaction pattern may be
expected for the pincer type compounds. From this point of view, the pincer
chemistry of main groups may be very interesting for further research in the field
of organometallic chemistry. This investigation will be based on using of new
pincer type ligands known from transition metals chemistry in the field of main
groups. Combination of intramolecular dative interaction mediated by one arm of
the pincer ligand with sterical shielding by the second one and thus building new
class of hybrid pincer ligands would be to our opinion also challenging for future
research. Using of these ligand systems will combine the best properties of steri-
cally demanding ligands and donating ability of pincer type ligands in one pot.
Main group metal compounds containing neutral pincer type ligands, which are
nearly unknown in this moment, seem to be next rational target in the field.
Especially recent excellent achievements by Prof. Milstein (e.g., see [107]) in the
field on transition metal derivatives of NNP or NPN systems are highly
inspirational for main group chemists and accommodation of low valent main
group metals within the cavity of such systems may lead to interesting and
unprecedented results.
Acknowledgments Support of the grant of the Grant Agency of the Czech Republic no. P207/10/
0130 is kindly acknowledged.
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202 R. Jambor and L. Dostál
Kálmán J. Szabó
Contents
1 General Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
2 Aldol Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
2.1 Aldol Reaction of Aldehydes and Isocyanides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
2.2 Reductive Aldol Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
3 Michael Additions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
4 Allylation of Aldehydes and Imines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
4.1 Pincer Complexes as Lewis-Acid Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
4.2 Allylated Pincer Complexes as Reactive Intermediates . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
1 General Considerations
2 Aldol Reactions
CH=O OH
Ph COOMe
cat. hydrolysis COOH
+ N COOMe
base O N Ph ð1Þ
NH 2
1a 2a 3a 4
R R
R = chiral functionality
Z M Z Z = heteroatom in the side arm
C O
N
OMe
H
5
Scheme 1 Reaction intermediate of the pincer complex catalyzed synthesis of oxazolidines 3a–b
O O
O O O O
Ph 2P Pt PPh 2 Ph2P Pd PPh2 N Pt N
OSO2 CF 3 Cl iPr
H2 O BF4
iPr
6 7 8
O O
O O
COOBn
N Pd N
t
BuS Pd StBu tBuS Pd StBu
O BF4 BF4
PF6
BnO MeCN MeCN
9 10
Scheme 2 Example for pincer complex catalyzed aldol reaction of aldehydes and isocyanides
CH=O
Ph COOMe Ph COOMe
[6]cat
+ N COOMe +
O N O N
7:3
ee = 65% ee = 3%
yield = 96%
1a 2a 3a 3b
platinum pincer complex 6 (Scheme 3). The reaction resulted in a mixture of two
diastereomers 3a and 3b up to 65 % ee. The major diastereomer, the trans form (3a),
could be obtained with a higher enantioselectivity than the syn diastereomer 3b.
Ortho substitution of the aromatic ring of aldehyde 1a led to the improvement of the
diastereoselectivity; however the enantioselectivity was decreased.
Pincer Complexes as Catalysts in Organic Chemistry 207
CH=O
Ar COOMe Ar COOMe
[7] cat
+ N COOMe +
AgOTf O N O N
86 : 14
ee = 26% ee = 71%
yield = 82%
1b 2a 3c 3d
Zhang and coworkers [22] replaced the metal atom of 6 with palladium and
implemented methyl groups in the side arms presenting complex 7. The catalyst
activated by silver triflate afforded cis and trans diastereomeric mixtures
(Scheme 4).
Interestingly, this catalyst gave the cis product in higher enantioselectivity than
the trans product. The best results (up to 71 % ee) were obtained using
mesitaldehyde 1b (Scheme 4). Van Koten and coworkers employed chiral NCN
palladium pincer complexes to achieve promising levels (up to 42 % ee) of
enantioselectivity [29]. Subsequent studies have shown that the diastereoselectivity
of the pincer-complex catalyzed reactions can be substantially improved by varia-
tion of the employed isocyanide. Thus Motoyama and coworkers [23] reacted
tosylmethyl isocyanide 2b with various aldehydes in the presence of phebox-
derived palladium and platinum (8) complexes (Scheme 5) to obtain exclusively
trans oxazolidine derivatives (3c). Similar to the above studies [21, 22] the degree
of the enantioselection was dependent on the structure of the aldehyde component.
The best result (75 % ee) was presented for the coupling of 2b with pivalaldehyde
1c. Interestingly, the same catalyst (8) provided low levels of diastereo- and
enantioselectivity, when isocyanide 2a was employed in place of 2b [23]. Further-
more, the platinum-based complexes seem to provide higher enantioselectivity than
the palladium analogs [24].
Van Koten and coworkers [25–27] have developed a new generation of easily
tunable chiral NCN-pincer-complex catalysts (such as 9) for aldol reaction of
aldehydes and isocyanides. These complexes are often easily accessible because
of the modern metallorganic techniques developed for their preparation. Although
the preliminary results for coupling of 1a and 2a display lower enantioselectivities
than the above-described complexes (6–8), further optimization of the reaction
208 K.J. Szabó
O O
Ph 2P Pd PPh 2 Ar COOMe
NTs X
CN COOMe + 10b
TsN N
Ar H rt
2a 3e
O O O O
+ CN COOMe
Ph2 P Pd PPh 2 Ph2 P Pd PPh2
2a
X C X
10b N 10c
COOMe
NMe2
Fig. 2 PCP-type complexes activate 2a by coordination to palladium [30], while NCN complexes
undergo insertion with 2a [29, 32]
O O
CH=O N Rh N
i AcO OAc i
Pr H 2O Pr
+ t 11 Et
CO2 Bu
Me2 PhSiH CO2 tBu
OH
ee = 97%, yield = 93%
1a 12 12b
Mechanistic studies by the van Koten [29, 32] and the Szabó [30] groups have
shown that the mechanism of the pincer-complex catalyzed aldol reactions is
strongly influenced by the electronic properties of the side arms (Fig. 2). In case
of p-acceptor side arms, such as in PCP complexes 10b, the isocyano group tightly
coordinates to palladium (10c) without affecting the integrity of the pincer-complex
structure. However, in case of s-donor side arms, such as in NCN (10d) or SCS
complexes, the isocyanoacetate is inserted to the Pd–C bond, such as in complex
10e. Accordingly, PCP complexes are direct catalysts to the aldol reactions with
isocyanates, while NCN (and related s-donor) pincer complexes are precursors of
the palladacyclic catalysts.
Nishiyama and coworkers [33] described a new type of asymmetric aldol reaction
catalyzed by phebox-derived pincer complex 11. In the so-called reductive aldol
reaction a,b-unsaturated esters are activated with hydrosilanes followed by metal
catalyzed condensation with aldehydes. Using benzaldehyde (1a) and tertiary-butyl
acrylate or crotylate (12) the reductive aldol condensation proceeds with remark-
ably high stereo- and enantioselectivity (Scheme 6). The main product (such as
12b) formed in excellent trans diastereoselectivity and the enantiomeric excess of
the reactions was typically over 90 %. In some of the greatest applications the
condensation product was obtained with 97 % ee and 93 % yield (Scheme 6) [33].
3 Michael Additions
Similar to the aldol condensations the Michael additions are also fundamentally
important reactions for carbon–carbon bond formation. Development and applica-
tion of pincer complexes (such as 13 and 14, Scheme 7) in Michael additions are
mainly concentrated to the area of asymmetric catalysis. In the usual form of the
210 K.J. Szabó
Ph Ph
O O N N
O O
N Pd N N Pd N
H H
H 2O SbF6 Cy TfO
Cy
OH HO
13 14
O O
[13]cat
+ CN
NC COOEt iPr
2EtN
EtOOC Me
ee = 34%, yield = 74%
15 16a 17a
O O
[14]cat
+ CN
NC COO iPr i Pr EtN
2 i
PrOOC Me
ee = 83%, yield = 91%
15 16b 17b
pincer-complex catalyzed process vinyl ketones (15) are reacted with a-cyanopro-
pionates (16a–b) to obtain the corresponding Michael adducts, such as 17a and 17b
(Schemes 8 and 9). The reaction is base catalyzed and the cyano group of 16 is
believed to coordinate the metal atom in the activated catalyst [24, 26, 34, 35].
The first asymmetric Michael addition was published by Richards and Stark
(Scheme 8) [24]. These authors employed oxazolinyl-based palladium pincer
complexes (13) as catalysts. These complexes catalyzed the Michael reaction of
15 and 16a with good yield, but with a moderate ee. The best enantioselectivity
(34 % ee) could be achieved using the cyclohexyl substituted complex 13
(Scheme 8). Considerable further efforts were taken [36, 37] for synthesis of
efficient oxazolinyl-based catalysts for Michael additions.
Ouzumi and coworkers [34, 35] have developed a new synthetic technique to
obtain sterically hindered chiral NCN complexes (such as 14), which proved to be
an excellent catalysts for Michael additions. This method is based on site controlled
metallation of the aromatic ring followed by introduction of the chiral ligand
Pincer Complexes as Catalysts in Organic Chemistry 211
1) Ph2 P Pd PPh2
OAc O POPh2
O 7b
Ph Ph
Ph 2PH +
Ph Ph 2) aq H2 O2
15c
up to 99% ee
15b
affording the desired pincer complex. Using this method several pyrroloimi-
dazolone derived pincer complexes (14) were synthesized [34, 35]. The enantios-
electivity of the Michael addition critically depended on the substituents of the
pyrroloimidazolone ring system. It was shown that the high enantioselectivity
requires the presence of hydroxy groups in the vicinity of palladium. It is suggested
that the hydroxy functionalities are directly involved in the enantioselection process
via hydrogen bonding. Employing catalyst 14 and isopropyl ester 16b the enantios-
electivity of the reaction could be increased to 83 % ee with excellent yield
(Scheme 9).
A nice example for asymmetric aldol addition was reported by Duan and
coworkers [38]. In this process diphenyl phosphine was reacted with chalcone in
the presence of the chiral PCP complex 7b (Fig. 3). This complex reported by
Zhang and coworkers [22] proved to be an efficient catalyst in asymmetric aldol
reaction (Sect. 2.1) as well. However, in the Michael addition excellent enantios-
electivity, up to 99 % ee, could be achieved. In subsequent studies 15b was replaced
by unsaturated N-acylpyrrole derivatives to broaden the synthetic scope of the
reaction [39].
Allylic alkylation is one of the most important metal catalyzed transformations for
selective synthesis of unsaturated organic species [1–3]. Several transition metal
species such as palladium, ruthenium, iridium, and rhodium catalyze allylation
reactions; however, in the most established processes nucleophilic reagents, such as
malonates and congeners, are allylated [40, 41]. Recently, however transition metal
catalyzed allylation of electrophiles, such as aldehydes and imines, received much
attention [42]. Pincer-complex catalysis proved to be a particularly useful tool for
rhodium- and palladium-catalyzed allylation reactions. From mechanistic point of
view the catalysts can be divided into two categories: Lewis-acid type catalysts and
allyl transfer catalysts. In Lewis-acid type catalysts the metal atom activates the
carbonyl group of the electrophile, while in allyl transfer catalysts the allyl moiety
is transferred from the metal atom of the pincer complex to the electrophile.
212 K.J. Szabó
O O
CH=O N Rh N
Cl Cl
Bn H 2O Bn OMe
+
SnBu3 18
OMe OH
ee = 80%, yield = 99%
1d 19a 20a
Nishiyama and coworkers [43, 44] have shown that phebox-based rhodium pincer
complexes (e.g., 18) readily catalyze the allylation of various aldehydes (1a and 1d)
using tributyl allyl stannane (19a) as allyl source (Scheme 10). The reaction
proceeds with high yields and good levels of enantioselectivity (up to 80 %).
Based on detailed X-ray studies and NMR experiments the authors concluded
that the reaction proceeds by Lewis-acid mechanism.
The key intermediate (21b) of the reaction [44] is generated by replacement of
the water ligand of 21a with the carbonyl group of the aldehyde substrate
(Scheme 11). Thus, the electron-deficient rhodium(III) center activates the aldehyde
molecule for electrophilic attack of allyl stannane 19a affording 22a, which is then
hydrolyzed to the homoallylic alcohol product. This step also recovers the catalyst
21c, which enters to the next catalytic cycle. Based on NMR studies [44],
transmetallation of 19a to 21a generating a new allylrhodium species could be
ruled out.
Palladium catalysis offers a versatile tool for allylic alkylation reactions [40, 41].
A vast majority of these reactions (Eq. 2) proceed via nucleophilic attack on (Z3-
allyl)palladium complexes (such as 24) generated from allyl acetates, chlorides or
related reagents (23) [2, 45–48]. The electrophilic character of the Z3-coordinated
allyl moiety is a prerequisite of the high reactivity toward nucleophiles leading to
allylated nucleophiles (25) as products. Electrophiles (such as aldehydes and
imines) can also be allylated using palladium catalysis by generating bis-
allylpalladium complexes (26) under catalytic conditions [42, 49]. This can be
realized by using allyl chlorides and allyl stannanes in the presence of catalytic
amounts of palladium (Eq. 2). The (Z3,Z3-bis)allylpalladium complexes (26a)
readily isomerize to the corresponding Z1,Z3-forms (26b), in which the Z1-allyl
moiety is nucleophilic, and therefore it can easily react with electrophiles (27)
affording allylated electrophile as product (28) [50].
Pincer Complexes as Catalysts in Organic Chemistry 213
O O
N Rh N
Cl Cl
R H 2O R
21a
- H 2O + R'CH=O
O O
N Rh N
Cl Cl SnBu 3
R O R 19a
H
R'
21b
R'CH=O
O O R'
N Rh N OSnBu 3
Cl Cl 22a
R R
21c
Scheme 11 Mechanism of the rhodium pincer complex catalyzed allylation of aldehydes [44]
Nu Nu
25
[Pd]cat
Lg
Pd
Lg = OAc, L L
SnR3
Cl etc. +L E
24 19a Pd
23 Pd
-L L ð2Þ
26a 26b
Pd E
L
28
E
27
electrophiles [57, 58], and the regioselectivity of the allylation is difficult to control
in the presence of allylic terminal substituents [55, 56]. Szabó and coworkers
[9, 59–63] employed pincer-complex catalysis to avoid the drawbacks caused by
formation of bis-allylpalladium complexes in palladium-catalyzed allylic substitu-
tion reactions. The basic idea (Scheme 12) was the replacement of the electron-
supplying Z3-allyl ligand of the Z1,Z3-bis-allylpalladium intermediates (26b) with
an electron-supplying pincer ligand (28). As in palladium pincer complexes only one
coordination site is accessible, the allyl moiety will coordinate in an Z1-fashion,
which is required to the nucleophilic reactivity [50].
A clear advantage of the Z1-allyl pincer complexes (28) over bis-allylpalladium
intermediates (26b) is that the spectator pincer ligand cannot be transferred from 28,
while the spectator Z3-allyl ligand of 26b can be removed by allyl–allyl coupling or
via isomerization to Z1-coordinated ligand followed by electrophilic attack.
Several pincer complexes [64–66] (such as 29–31) proved to be active catalysts in
electrophilic allylation reactions (Scheme 13) [59–63, 67]. In these reactions aldehydes
(Scheme 14) (such as 1e and 1f) are readily allylated (Schemes 14 and 15) with allyl and
cynnamyl stannanes (19a–b). Wendt and coworkers [68, 69] have shown that pincer-
complex catalysis can be employed for allylation of carbon dioxide. In these reactions
also Z1-allyl pincer complexes (such as 28) were suggested as key-intermediates.
Allylation of sulfonimines (e.g. 32a) could also be carried out smoothly (Scheme 16)
with both allyl stannanes (19a-b) and allyl trifluoroborates (33a). The reactions display
Pincer Complexes as Catalysts in Organic Chemistry 215
yield = 77%
32a 33a 34a
a high level of functional group tolerance as keto, nitro, cyano, and carbethoxy
functionalities remained unchanged in the allylation reactions.
Using cinnamyl substrates (e.g., 19b and 33a) the reaction proceeded with a high
level of regio- and stereoselectivity (Schemes 15 and 16). Interestingly, allylation of
the aldehydes proceeds with anti-selectivity, while the allylation of imines gives syn
diastereoselectivity. The different stereoselectivities could be explained by the struc-
ture of the TS geometries of the reaction, which were modeled by DFT calculations
[70]. It was found that the catalytic activity was also dependent on the structure of the
pincer-complex catalysts. Complexes with PCP ligands displayed higher activity than
NCN complexes [59]. Complex 29 proved to be very stable under the catalytic
conditions and showed higher activity than 30 and 31 [59, 60].
The asymmetric version of the allylation of imines has also been developed [63, 71]
using chiral pincer-complex catalysts such as 35 and 36 (Scheme 17). This reaction
affords enantioenriched homoallylic sulfonamides, which can easily be converted to
the corresponding amine product. It was shown that g-substitution of the BINOL
ligand leads to increase of the enantioselectivity of the reaction. Unfortunately, the
TADDOL-based complex 36 gives very low levels of enantioselectivity. The best
results (up to 85 % ee) were reported using bis-phenantrole complex 35b (Eq. 3) The
van Koten group [72] obtained promising levels of enantioselectivity by asymmetric
216 K.J. Szabó
Me Me
O O
O O
P Pd P
O O
I
Me Me
35a
O O
O O
P Pd P
O O
I
35b
Ph O O Ph
O P Pd P O
Ph Ph
O I O
O O
Ph Ph
O Ph Ph O
36
allylation of sulfamoyl imines, while the Bedford group [73] presented asymmetric
allylation of aldehydes using pincer-complex catalysis with good ee.
CHNSO2 Ph
NHSO 2Ph
SnBu 3 + [35b]cat *
ð3Þ
up to 85% ee
19a 32b 34b
The mechanistic aspects of the allylation reactions (Scheme 18) were investigated
by NMR and DFT modeling studies [60, 61, 70]. The NMR studies clearly showed
that the introducing step of the catalytic reaction is transmetallation of the allyl
stannane (19a) or allyl trifluoroborate substrate (33a) with the pincer-complex catalyst
(29) generating (Z1-allyl)palladium pincer-complex intermediate 35. DFT modeling
studies indicate that the Z1-allyl moiety of this complex undergoes electrophilic attack
with the imine (32a) or aldehyde (1) electrophiles with a remarkably low activation
barrier [60, 70]. This step determines the regio- and stereoselectivity of the process,
which could be rationalized on the basis of DFT calculations [60, 70]. The
transmetallation and electrophilic attack has an opposite electron demand, which
requires a careful optimization of the electronic properties of the employed pincer-
Pincer Complexes as Catalysts in Organic Chemistry 217
Bu 3Sn
NTs
Q O O SnBu3
37
Ph2P Pd PPh2 19a
OCOCF3
29 transmetalation
XSnBu3
XSnBu3
O O O O
Ph 2P Pd PPh2 Ph2 P Pd PPh2
s
NT
35
Q 36
electrophilic
attack
PhCH=NTs
32a
Scheme 18 Catalytic cycle for allylation of imines via (Z1-allyl)palladium pincer complex
intermediate [60, 70]
complexes are usually able to both create and cleave carbon–metal bonds [74–78].
Therefore, when synthesis of organometallic species is desired, the electronic
properties of the catalyst have to be carefully tuned to avoid carbon–metal bond
cleavage of the products. As it was pointed out in Sect. 1, the tight metal–ligand
bonding allows an efficient tuning of the pincer reactivity of pincer complexes; and
thus some of these species are excellent catalysts for selective synthesis of
allylboranes, allyl stannanes, allenyl and propargyl stannanes, and silanes.
Scheme 19 Pincer complexes employed for preparation of unsaturated allyl, allenyl and
propargyl metal species
SO 2Ph
N [31b] cat NHSO Ph
+ [B(OH) 2]2 2
B(OH)2
Ph Ph
40 39 41a
KHF2
NHSO 2Ph
BF3 K
Ph yield = 81%
33b
Scheme 20 Boronation of vinyl aziridine to obtain organoboronic acids and trifluoroborates [80]
[31b]cat [31b]cat
Ph OH 39 Ph B(OH) 2 39 Ph OAc
ð4Þ
42b 41c 43
faster
PhI EtOOC
[Pd(0)]cat EtOOC Ph
yield = 91%
45
Scheme 22 Employment of boronic acids in palladium(0) coupling with aryl iodides [81]
COOMe COOMe
[31b] cat
+ CH=O
OH 39
B(OH)2
42a 1g 41b
COOMe
H
OH
yield = 71%
46
Scheme 23 One-pot reaction for highly diastereoselective allylation of aldehydes with allyl
alcohols [83]
alcohols (41b) can be prepared starting from easily accessible reactants (42a).
Subsequent studies have shown that the Petasis [94, 95] borono-Mannich reaction
can also be combined with the catalytic borylation [84]. It was shown that
a-aminoacids can be prepared from allyl alcohols by pincer-complex catalyzed
borylation followed by the Petasis reaction in a one-pot sequence. Furthermore,
ring-closing metathesis and pincer-complex catalyzed borylation–allylation can
also be performed as a one-pot reaction resulting in stereodefined carbocyclic
products [86].
O [38]cat SnMe3
+ (SnMe 3) 2 OH
HO OPPh 2
yield = 59%
48 47 49a
NHSO2 Ph
[38]cat [29]cat
COOEt Me3 Sn COOEt
47 32b Ph
Cl COOEt
yield = 56%
50 49b 51
Scheme 25 One-pot reaction for allylation of sulfonimines with allyl chlorides using NCN
complex 38 and PCP complex 29 to catalyze the consecutive steps [62]
47
Ph
CH=O R
R
51b
Fig. 4 One-pot reaction for allylation of aldehydes with allyl chlorides using a single pincer-
complex catalyst 38b [97]
shown [100, 101] that using NCN complex 38 as catalyst hexamethylditin (47)
undergoes substitution of propargylic substrates instead of addition of the
distannanes to the triple bonds (Scheme 26).
The reactions are highly selective and stannylation of secondary propargyl
chlorides (52a) results in exclusively allenyl stannane products (such as 53a)
[101]. In case of primary propargyl chlorides the regioselectivity is determined
by the substituents directly attached to the triple bonds [100, 101]. Propargyl
epoxides can also be employed as substrates in the substitution reactions [101].
Thus, stannylation of cyclic epoxide 52b proceeded with excellent allenyl selectiv-
ity and high anti-steroselectivity affording 53b as product (Scheme 27). In the
stannylation reactions SeCSe pincer complex 31b also proved to be a highly active
catalyst; however, in some reactions it gave lower propargyl to allenyl
regioselectivity than NCN complex 38.
Pincer Complexes as Catalysts in Organic Chemistry 223
Cl
+ (SnMe 3) 2 [38] cat Me3 Sn
NHBoc NHBoc
yield = 95%
52a 47 53a
OH
O SnMe3
[38]cat
+ (SnMe3 )2
yield = 95%
52b 47 53b
THF-d8
+ (SnMe 3) 2 + Me 3Sn-OAc
Me2 N Pd NMe2 Me2 N Pd NMe2
OAc SnMe3
47 56
Scheme 29 Stoichiometric reaction indicating the transfer of trimethylstannyl group to palladium [101]
Q
(SnMe 3) 2
Me3 Sn Me2 N Pd NMe2 47
L
Cl Me2 N Pd NMe2
Q Me3 SnL
SnMe3
56
47 and 39) may require opening of the side arm of the catalyst, which is easier in
NCN and SeCSe complexes than in PCP ones.
Kharasch and coworkers [102, 103] extensively studied (Eq. 5) the addition of
organohalides to terminal alkenes (57). In case of chlorinated substrates (such as 58)
the addition requires peroxide catalysis affording the anti-Markovnikov product such
as 59a (Eq. 5). The reaction proceeds via radical mechanism, which is classified as
“atom transfer radical addition” (ATRA). A limitation of the peroxide catalyzed
process is the difficult control of the product distribution, as formation of 59a is
usually accompanied by telomerization and polymerization reactions occurring via
common radical intermediates.
cat. Cl
R + CCl4 Cl3C ð5Þ
R
57 58 59a
Van Koten and coworkers [104–108] have found that the product distribution of the
Kharasch reaction can be controlled by using nickel pincer-complex catalyst 60
(Eq. 6, Scheme 31). Employing this catalyst the addition reaction leads exclusively
to the 1:1 adduct (such as 59b) without formation telomerization and polymeriza-
tion products (Eq. 6).
[60a] cat Cl
COOMe + CCl4 Cl3C
COOMe ð6Þ
61 58 59b
The reaction is very robust and the high selectivity is maintained employing a
wide variety of substrates [106]. The reactivity of the catalyst could be efficiently
tuned [109] by substitution of the para position of 60a (such as 60b) and by
changing the steric bulk of the substituents in the side arms [104]. It was found
that electron-donating groups, such as methoxy (60b) and dimethyl-amino groups,
increase the reactivity of the complex, while electron-withdrawing substituents
226 K.J. Szabó
decreased the catalytic activity. Replacement of the methyl groups in the side arms
with isopropyl groups led to reduced catalytic activity probably because of steric
interactions [104].
The high catalytic stability and tunability of 60a makes it particularly suitable
for binding to various supports to obtain recyclable catalysts. Van Koten and
coworkers [105, 110] have shown that nickel palladium complexes can be attached
to carbosilane dendrimers such as 62. Application of these dendrimer catalysts in
membrane reactors allows, in principle, a continuous catalytic process [110].
Dendrimer 62 proved to be an active catalyst in the Kharasch reaction of 61 with
carbon tetrachloride 58 for selective formation of adduct 59b and the catalyst could
be recovered by filtration (Scheme 32).
Based on kinetic measurements and spectroscopic studies van Koten and coworkers
[106] proposed a catalytic cycle for the pincer-complex catalyzed Kharasch reac-
tion (Scheme 33). Accordingly, the catalytic cycle is initiated by a single electron
transfer (SET) from the nickel atom of 60c to carbon tetrachloride 58. This step
proceeds via activated complex 63a, which undergoes oxidative addition to nickel
(IV) complex 63c followed by fragmentation to give nickel(III) complex 63d and a
trichloromethyl radical. An interesting feature of this process is that it takes place in
the absence of a free coordination site on the nickel atom of 63c. The three species
63a–c involved in this process are in a fast equilibrium. It was suggested that
electron-donating para substituents (such as in 60b) are able to stabilize Ni(III)
complexes (such as 63d), and therefore these substituents increase the catalytic
activity of the complex. The next step is the addition of the trichloromethyl radical
to the terminal alkene leading to complex 63e. According to kinetic measurements
this is the rate-determining step of the catalytic process. In the next step complex 63
undergoes reversible SET from the radical carbon center to nickel producing adduct
64 and recycling the catalyst 60c.
Cl
Me2
Me 2 Me2N Ni NMe2 N Cl
Cl N
Ni
Ni
NMe2
Me2N
Me2Si Me2Si
SiMe2
Me2 Me2
Cl N N
Me Me Cl
Ni Si Ni
Me2Si
Me2N Si Me2
NMe2
Me2S i Si
Si Me 2
Me2Si SiMe2
Me2N NMe2
Me Me
Cl Ni S iMe2 Si Si Si Si Si Me2Si Ni Cl
Me Me
Me2N NMe2
Me2Si SiMe2
Si
Me2Si SiMe2
Me 2N Me2Si NMe2
Ni SiMe2
Si Ni
Cl Me Me
N N Cl
Me2 Me2
Me2Si
SiMe2 SiMe2
NMe2
Me2N
Ni
Ni Cl
Cl N
N Me2N Ni NMe2 Me2
Me2
Cl
62
Scheme 32 Example for dendrimer supported nickel pincer complex catalyst [105]
Because of the extremely high importance of the Heck and Suzuki coupling
reactions in both industrial and laboratory scale synthetic organic chemistry con-
siderable efforts have been invested to obtain new efficient catalysts. In this work
one of the most important factors is the development of new durable catalysts with
high turnover number (mol product/mol catalyst, TON). Thus, a huge number of
228 K.J. Szabó
CCl4
58
II
Me2 N Ni NMe2
X II
Me2 N Ni NMe2
60c
X Cl
R1 CCl3
Cl3C 63a
Cl
R2
64
IV X III X
Me 2N Ni NMe 2 Me2 N Ni NMe 2
Cl3C Cl Cl
Cl3C
63c 63d
III X
Me 2N Ni NMe 2
1
R Cl
Cl3 C
R2 63e
R1
R2
Scheme 33 Catalytic cycle for the pincer complex catalyzed Kharasch addition of carbon
tetrachloride to terminal alkenes [106]
pincer complexes were prepared and applied as catalysts in Heck and Suzuki
coupling reactions. Some of these catalysts are characterized with very high
TONs (up to [113] 9 106). The most important basic skeletons of pincer-complex
catalysts employed in these reactions are given in Scheme 36.
Milstein and coworkers [7, 113] reported the first pincer-complex catalyzed
Heck reaction of various aryl iodides and bromides (65) with various acrylate esters
(such as 66) to obtain styrene derivatives (cf. Scheme 34). In these reactions PCP
complex 70 and its analogs were employed as efficient catalysts. The yields of the
products were often quantitative and TONs up to a 5 105 could be achieved.
Jensen and Morales and coworkers [114, 115] employed phosphinito PCP
complex 71 for Heck coupling reactions. It was shown that the phosphinito PCP
complexes (such as 71) are more active catalysts in Heck coupling than the
phosphino analogs (such as 70). For example, the phosphinito complex 71 is able
to couple aryl chlorides (65, X ¼ Cl) [115], while the synthetic scope of phosphino
complexes (such as 70) is limited to aryl iodides and bromides. Interestingly, aryl
bromobenzene (76) undergoes (Scheme 37) a double Heck coupling with styrene
(77) and other terminal olefins to give trisubstituted olefins (78) [114]. Shibasaki
and coworkers [116] succeeded to increase the catalytic activity of complex 71 by
replacement of the isopropyl groups with methyl hydroquinone substituents to
obtain catalyst 72. Although this catalyst required relatively high reaction
Pincer Complexes as Catalysts in Organic Chemistry 229
X R
[Pd]cat
+ COOMe
base COOMe
R
65 66 67
X B(OH) 2
[Pd]cat
R
+ base
R
65 68 69
MeO
OMe
O O O O
iPr PiPr2 iPr2 P PiPr 2 O P P O
2P Pd Pd Pd
O O
OCOCF3 Cl I
70 71 72
MeO OMe
N N N N Pd N
PhS Pd SPh Pd
N N N N
Cl
73 74 75
Scheme 36 Pincer complex architectures active catalysts in Heck and Suzuki coupling reactions
Br
+ [71] cat
2
76 77 78
complexes, and therefore the applied pincer complexes are probably just precursors
of highly reactive palladium catalysts (see Sect. 6.2) of the Heck coupling.
Crabtree and coworkers [119, 120] reported the synthesis of several carbene
ligand-based CNC (74) and CCC (75) pincer complexes. In these complexes the
metal atom is even more tightly bound to the ligand than in traditional pincer
complexes with heteroatoms in the side arms, which lends a particularly high stability
and durability for these complexes. Because of the high stability, these complexes
could be employed for Heck coupling without employing an inert atmosphere.
Complex 74 performed [120] much better in Heck couplings than its CCC analog 75.
Dupont and coworkers [8, 121] employed mixed PCN and SCN pincer
complexes as catalysts in Heck coupling reactions. These complexes usually
perform better than the other phosphine free pincer complexes with TONs (up to
106). Based on kinetic studies it was concluded that the mixed PCN and SCN pincer
complexes are not the active catalysts of the Heck coupling reactions, but they serve
as reservoirs for catalytically active Pd(0) species [121].
Bedford and coworkers [64] reported the synthesis of PCP complex 29
(Scheme 13) and its application in Suzuki coupling reactions (Scheme 35). In
these reactions phenylboronic acid (68) could be efficiently coupled with
bromoacetophenone (65, X ¼ Br, R ¼ COMe) and some other substrates. The
reactions performed at relatively high temperature (130 C) proceeded with excel-
lent TONs and with usually high yields. Dupont and coworkers [122] studied the
SCS pincer-complex catalyzed Suzuki reaction of bromotoluene (65, X ¼ Br,
R ¼ Me) with phenylboronic acid (68). The catalyst performed well; however,
the catalytic activity is lower than that for PCP complexes, such as 29.
Frech and coworkers performed several successful applications for Heck,
Suzuki, and Sonogashira coupling reactions using aminophosphine-based pincer
complexes [123–126]. The same group has performed DFT modeling studied to
gain mechanistic insights into the mechanism of the pincer-complex catalyzed C–C
coupling reactions.
(Scheme 34). However, in palladium pincer complexes (e.g., 70–75) the palladium
atom is in one of the most stable oxidation states +2. Reduction of the central atom
for carbon–palladium bonded complexes (with exception of CNC carbon complex
74) usually involves a complete decomposition of the complex under catalytic
conditions. It should be however noted that Milstein and coworkers [123] have
shown that in some cases the reduction of the palladium atom to Pd(0) can be
reversible. On the other hand, oxidation of palladium(II) to palladium(IV) requires
a high activation barrier, and therefore the +4 oxidation state is relatively unusual in
palladium-catalyzed processes [2, 41, 111]. In this section, we focus on the mecha-
nism of the Heck reaction; however, the same type of mechanistic problems arises
in other coupling reactions involving aryl halides, such as in Suzuki coupling.
In the classical (i.e., not pincer-complex catalyzed) Heck coupling reaction
(Scheme 38) the catalytic cycle is initialized by the oxidative addition of the
palladium(0) catalyst (79) to the carbon–halogen bond of the aryl halide substrate.
This process results in a palladium(II) aryl species (80), which undergoes insertion
reaction with the activated alkene to give adduct 81. The last step of the catalytic
cycle is b-hydride elimination of 81 involving reduction of the palladium atom to
recycle the catalyst (79) and to provide the coupling product. Thus, this catalytic
cycle involves an oxidation step (79 ! 80) and a reduction step (81 ! 79).
However, such a Pd(0) ! Pd(II) ! Pd(0) cycle is not possible for XCX (X ¼
heteroatom) type of pincer complexes, which decomposes when the palladium
atom enters to zero oxidation state [118, 127, 128].
As an alternative to the traditional Pd(0) ! Pd(II) ! Pd(0) (Scheme 38)
sequence a Pd(II) ! Pd(IV) ! Pd(II) cycle was suggested [113, 115]
(Scheme 39), since palladium(IV) pincer complexes are supposed to be stable
species. According to this mechanism (Scheme 39) the alkene substrate undergoes
oxidative C–H activation with the employed pincer-complex catalyst (such as 71)
to give palladium(IV) species 82, followed by reductive elimination of HCl
affording vinyl palladium(II) complex 83. The next step is a further oxidative
addition of the aryl halogenide, such as chloride, to give complex 84. Reductive
elimination of the coupling product from 84 regenerates the catalyst (71), which
may enter in the next catalytic cycle. Several experimental findings seem to support
this Pd(II) ! Pd(IV) ! Pd(II) cycle such as the apparently high stability of
palladium pincer complexes under the catalytic conditions, the dependence of the
232 K.J. Szabó
Ar
O O
II
i
Pr 2 P Pd PiPr 2 R
R
reductive Cl
oxidative
elimination 71 addition
O O O O
IV Cl IV Cl
i
Pr 2P Pd PiPr2 i
Pr2 P Pd PiPr 2
Ar H
R 84 R 82
O O
i
II
Pr 2 P Pd PiPr 2 HCl
Ar-Cl
oxidative reductive
addition elimination
R
83
Scheme 39 Proposed catalytic cycle for the Heck coupling involving Pd(IV) intermediates [115]
catalytic activity on the pincer-complex structure (Sect. 6.1), the high TON, as well
as the surprisingly high reactivity of 71 for activation of aryl chlorides.
On the other hand, several recent studies pointed out that despite the high
thermic and air stability of the pincer complexes partial or complete decomposition
to palladium(0) species takes place under the reaction conditions of the Heck
coupling [8, 11, 111, 118, 121, 127, 128]. These studies are based on kinetic studies,
poisoning experiments, Hg(0) trapping of palladium(0), and NMR measurements. It
was concluded that the decomposition of pincer complexes leads to the formation of
highly active palladium(0) species. Accordingly, pincer complexes do not catalyze
the Heck reactions themselves (such as in Scheme 39), but release active palladium
(0) species, which catalyze the coupling reaction according to the classical catalytic
cycle (Scheme 38). Jones and Weck and coworkers [127] studied the decomposi-
tion process of pincer complexes under the Heck conditions. These authors found
(Scheme 40) that the employed base plays a very important role in degradation of
the otherwise very stable PCP complexes (such as 30c). It was suggested that
triethyl amine or other bases employed in the catalytic process coordinate to
palladium decoordinating one of the side arms of 30c affording complex 85. This
complex is able to undergo irreversible b-elimination with one of the
carbon–hydrogen bonds of the triethylamine ligand resulting in anionic complex
86, which subsequently generate the active palladium(0) catalyst. Cámpora and
coworkers [129] have shown that the Pd(II) atom of simple PCP complexes
undergoes reduction to Pd(0) species in MeOH under mild conditions. These
authors were able to isolate and characterize the resulting Pd(0) complexes.
Pincer Complexes as Catalysts in Organic Chemistry 233
R R R
PPh 2 PPh2
Et3 N
Ph 2P Pd PPh2 Ph2 P Pd NEt2 Ph2 P Pd H +
Cl Cl Cl
Et2 N
30c 85 86
Scheme 40 Proposed initial steps of the decomposition of PCP complexes under Heck conditions [127]
OAc
OAc R I X [29]cat.
+ OAc
OAc NaHCO3
50°C R
77b 86c
R
86b
As mentioned above several findings supporting [113, 115, 126] that the Heck
reaction of aryl halogenides with alkenes might proceed through Pd(IV) pincer
species (Scheme 39). However, the scientific community tends to accept [8, 11,
111, 118, 121, 127, 128] that in most of these reactions pincer complexes serve as
precatalysts for the Heck coupling reactions providing palladium(0) species, which
are the active catalysts. Nevertheless, replacement of the aryl halides with strong
oxidants, such as hypervalent iodines (Fig. 5), or application of chelating aryl-
halogenides (Fig. 6) may open new synthetic routes for Heck couplings via Pd(IV)
species rendering pincer complexes to the direct catalysts of these reactions.
For example the Szabó group [130] has developed a Heck coupling reaction of
alkenes with hypervalent iodine 86b (Fig. 5). Several findings supported the lack of
Pd(0) intermediates in this process. Thus, the integrity of the pincer-complex
catalyst completely retained under the reaction and mercury poisoning of the
catalyst was not observed. The process was exploited to Heck coupling of allyl
acetates (such as 77b). These allylic species are known to undergo oxidative
addition with Pd(0), which was not observed in this process. DFT modeling studies
also supported the assumption of the oxidative addition of hypervalent iodines
(such as 86b) to pincer complexes. In subsequent studies the Szabó group further
developed this concept and presented several related studies for C–H acetoxylation
[131] and borylation [132] by pincer complexes. Formation of Pd(IV) pincer
complexes could be detected under the catalytic conditions, when NCN complex
38 was reacted with hypervalent iodonium salts, such as PhI(OAc)2 [131] and PhI
(OCOCF3)2 [132].
234 K.J. Szabó
I
COOMe
MeO CO 2H
O
N
O
MeO Pd 86d (10 mol%) COOH
I +
O AgClO4 + AgI + HClO4
rt, dark, 6 h
83%
COOMe
86d
Fig. 6 Pd(IV) oxidation state is stabilized by a chelating aryl group [133, 134]
Vicente and coworkers [133, 134] have shown (Fig. 6) that in the presence of
AgClO4 ortho-iodobenzoic acid and methyl acrylate undergo Heck coupling via Pd
(IV) intermediate 86d. The chelating ligand arising from ortho-iodobenzoic acid
stabilizes the Pd(IV) complex and AgClO4 hinders the reductive elimination of the
iodoaryl precursor. Species 86d arises from the oxidative addition of the aryl iodide
to the parent Pd(II) pincer-complex species.
t
BuN Pd NtBu
CH3 cat PhHN
86
+ PhNH3 BPh 4
CN CN
87 88 89
tBuN Pd N tBu
CH3
86
CH 4 PhNH 3
90
CN
tBuN Pd N tBu
89 87
NH2 Ph
91
90
NC
92 CN
93 NH2 Ph PhNH 2
Scheme 42 Proposed catalytic cycle for pincer complex catalyzed hydroamination [7, 135]
N
Ph2 P Pd PPh2
Cl Cl cat
CBz
CBz 95 CBz
N H Pd(MeCN)2 Cl2 N
NH
O
Cu(OTf)2
AgBF4 Cu(OTf) 2
yield = 98%
97 94 96
O OH [Ru]cat OH O
+
base
+ ð7Þ
R R' R R'
98 99 100 101
tBu N
Cl Ph Cl
(C 6F5 )2 P Ru P(C 6 F5) 2 Ph P Ru P H2 N Ru
tBu PPh2
Ph3 P Ph3 P Cl
Ph 2P
Scheme 44 Ruthenium pincer complexes applied as catalysts for transfer hydrogenation reactions
[141–143, 146]
the ketone substrate prior to the hydrogen transfer, and therefore the catalytic
activity is increased.
Van Koten and coworkers [141] studied the mechanistic aspects of the transfer
hydrogenation reactions. It was found that when 103b was heated in isopropanol in
the presence of base (KOH) hydrido complex 107 was formed (Scheme 45), which
was considered as the active intermediate of the reduction of ketones.
classical metal salt catalyzed transformations. The chemo-, regio-, and stereose-
lectivity of the pincer-complex catalysts could be effectively tuned by changing the
heteroatoms in the side arms and substitution of the para position of the complexes.
Based on the large number of recently published pincer-complex catalyzed
reactions it can be predicted that the number of new applications with pincer-
complex catalysts will considerably increase in the next couple of years. The
main targets are those carbon–carbon, carbon–nitrogen, and carbon–metal bond
formation reactions, which are not amenable with traditional transition metal
catalysis due to selectivity or reactivity issues. The design of new chiral pincer
complexes for asymmetric catalysis is probably a very important area. The stable
structure and well-defined stoichiometry of pincer complexes allow a rational
design of effective chiral catalysts. Another important area is the immobilization
of pincer complexes on solid support or dendrimers to obtain robust, recyclable
catalysts. The strong metal bond interaction helps to create stable non-leaching
catalysts, which can be employed several times in an economical way.
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240 K.J. Szabó
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2 Preparation of Transition Metal Complexes with Phebox Ligands . . . . . . . . . . . . . . . . . . . . . . . 246
2.1 Group 9 Metals (Rh, Ir) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
2.2 Group 10 Metals (Ni, Pd, Pt) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
2.3 Group 8 Metals (Fe, Ru) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
2.4 Group 11 Metals (Au) and Early Transition Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
2.5 Molecular Structures of Phebox Metal Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
1 Introduction
Anionic meridional ligands, such as PCP and NCN pincer ligands, can produce
transition metal complexes that serve as highly reactive catalysts in homogeneous
reactions [1–3]. Pincer transition metal complexes consist of a metal–carbon
covalent bond and two metallacycles, which may stabilize the metal center and
create unique electronic properties and steric environments. An additional advan-
tage of the pincer ligand is the tunability of the molecular structure. This feature is
useful for designing optically active catalysts. As shown in Fig. 1, chiral PCP and
NCN ligands containing benzene backbones have been developed using several
types of chiral sources to control the chiral reaction site. For example, Venanzi et al.
introduced C-stereogenic centers at the benzyl positions to prepare the chiral Pt
complex A [4]. Similar PCP and NCN ligands containing C-stereogenic centers
were utilized in the Pd and Pt complexes B–C [5, 6]. Introduction of chiral centers
at the coordinating position, such as P and N donors, expanded the diversity of the
ligands. Chiral NCN ligands bearing hexahydro-1H-pyrrolo[1,2,c]imidazolone [7],
tetrahydroquinoline [8], pyrrolidine [9], and imidazoline fragments [10] were
applied to the preparation of the Pd(II) and Pt(II) complexes D–G. Phosphorus
donors, namely phosphoramidite [11, 12] and phosphite fragments [13–15], were
introduced into the PCP ligand framework to construct the Pd complexes H–I. In
addition, PCP pincer ligands with P-stereogenic centers produced the Pd [16], Ir
[17], and Ru complexes J–K [18]. The Pd and Pt complexes described earlier
served as asymmetric catalysts in aldol reactions of aldehydes with isocyanoacetate
[5, 8, 9], allylation of aldehydes or imines with allylic stannanes [11, 13, 14],
Friedel–Crafts alkylation of indoles with nitrostyrene [10], Michael addition of a-
cyanoesters to enones [7], Mannich reaction of imines with benzyl nitriles [15], and
hydrophosphination of enones [19].
Optically Active Bis(oxazolinyl)phenyl Metal Complexes as Multipotent Catalysts 245
t Bu
R' R'
O O
O O
* * * * N N
O O
Ph2P PPh2 E E N N N N
M M H Pd H Pd
Cl M = Pd, Pt Cl Cl R Br R
R R
B: E = PPh2, M = Pd, Pt
A D E
C: E = NMe2, M = Pt
R' R'
N N O O
N N N N O P P O
Pt M Pd
R R O O
OTf Cl X
F G H
M = Pd, Pt
O O t Bu t Bu
N N t Bu Ph Ph Ph
P P P P P P P P
Pd Pd Ir Ru
Ph O O Ph Ph t Bu Ph t Bu Ph tBu
Ph Cl Ph Cl H Cl PPh3
Cl
I J K L
O N O O O
N N N N
M M
R R R R
pybox phebox
i) [Rh(coe)2Cl]2
O O ii) CCl4 O O O O
Cl X
N N or N N N N
SnMe3 Rh Rh
RhCl3·3H2O
R R R Cl R R X R
2 CH2Cl2,rt OH2 OH2
R = iPr (1-ip) 4 (X = OAc)
RhCl3·3H2O sBu (1-sb) 5 (X = Br)
O O MeOH, reflux tBu (1-tb) 6 (X = F)
N N or Ph (1-ph)
[RhCl(coe)2] 2 Bn (1-bn)
R R CHCl3
3
Me 6 4 Me Me 5 3 Me
Rh: RhCl3·3H2O
NaHCO 3, MeOH
O O O O
50 °C, 3 h
Cl
N N Ir: IrCl3·3H2O or N N
M
iPr iPr H2IrCl5 iPr Cl iPr
7 NaHCO3, iPrOH OH2
reflux, 10 h 8 (M = Rh) 84%
9 (M = Ir) 61%
O iPr O iPr
N N
RhCl3·3H2O Cl
O (CH2)11 O O (CH2)11 O Rh OH2
DMF/MeOH Cl
N N
O iPr O iPr
O O O
R' N N
N R RhCl3·3H2O Cl R Cl
Rh or Rh
N R EtOH, reflux Cl R Cl
R' N N
O O O
10 11 12
R = Me, Et, iPr, iBu, tBu, Ph
Bergman and Tilley designed a phebox analogue, the novel C2-symmetric bis
(oxazoline) pincer (benbox) ligand (10), in which a wider N-Me-N bite angle was
expected [32]. Cyclometalation of the benbox ligand with RhCl3·3H2O resulted in
the formation of the (benbox)RhCl2 complexes 11 in 8–59 % yields (Scheme 4).
Although the related (phebox)Rh complex was a coordinatively saturated 18-
electron complex with coordination of a H2O molecule, the (benbox)Rh complex
11 was found to be a coordinatively unsaturated complex with the Rh center
adopting a square pyramidal geometry. Interestingly, in the case of bulky ligands,
the unique (benbox)Rh(II) complex 12 was also produced. In complex 12, the
geometry of the Rh atom was determined to be square planar.
O O O O
Cl
N N N N
Pt Pt
iPr iPr iPr iPr
Cl Cl OH2
16 15
O O K2PtCl4 O O
N N AcOH, reflux N N
Pt
49%
1-dm Cl
13-dm
O O (dba)3Pd2(H2O)2 O O
N Br N benzene, D N
Pd
N
R R 87% (R = tBu) R R
17 X
18 (X = Br)
19 (X = Cl)
O O PdCl2(PhCN)2
N N CH2Cl2, 0°C +
SnMe3
R R 96% (R = iPr) O O
2
AgBF4, N N
Pd
AgOTf, R R
O O or OH2
i) LDA, TMEDA
AgSbF6
20
N N ii) PdBr 2(cod)
R R 41% (R = Me)
3
i) (COCl)2, DMF
CH2Cl2, 25 °C, 6 h
ii) aminoalcohol, NEt 3 O O
HO 2C CO 2H
Pd(PPh3) 4 CHCl3, 25 °C, 12 h
HO2C CO2H N N
AcOEt Ph3P Pd PPh3 Pd
iii) MsCl, NEt 3, O2
Br reflux, 24 h iPr iPr
Br CHCl3, reflux, 12 h Cl
21 93%
22 19
57%
Richards reported the first preparation of a (phebox)Ni complex 24, which was
obtained by oxidative addition of (phebox)I 23 to Ni(cod)2 in 70 % yield (Scheme 8)
[37]. Similarly, the chiral (phebox)Br 17 was used to prepare the (phebox)NiBr
complex 25 in high yield [38]. The Ni complex 25 was also synthesized by
transmetalation of in situ generated (phebox)Li with NiBr2(PEt3)2. The latter
reaction produced a side product, NiBr(phebox)(PEt3)2, which contained a
monodentate coordinated phebox ligand.
The properties of the phebox metal complexes could be controlled by
substituents on the benzene backbone of the ligand. Connell et al. prepared a series
of phebox ligands containing methoxy groups and their Ni and Pd complexes
(Fig. 3) [39].
i) LDA
O O TMEDA O O Ni(cod)2 O O
N N i) I2 N I N toluene N N
Ni
1-dm 42% 70%
23 I
24
Ni(cod)2
O O O O
THF
N Br N or N N
Ni
i) nBuLi, Et2O
R R R R
17 ii) NiBr2(PEt3)2, THF Br
25
OMe OMe
MeO OMe MeO OMe
O O O O O O
N N N N N N
M M M
iPr iPr iPr iPr iPr iPr
X X X
M = Ni, Pd, X = Br, I
RuCl3(H2O)3
O O O O
O O Zn, cod Na(acac)
R' R' N N
N N EtOH, reflux N N Ru
Ru OC
3 OC R O R
R R R Cl R O
Cl
RuCl3(H2O) 3 Zn
NaOAc
Mg, cod Cl
R Cl R
EtOH, reflux 28
Ru
N N
CO
O O
O O O O
R' R' N N
N N Ru
Ru 26 OC
OC Cl R O R
R R O
OH2
27
29
O O Fe2(CO)9 O O
N Br N toluene, 50 °C, 3 h N Br N
Fe
iPr iPr 69% iPr CO iPr
17 CO
30
Preparation of a gold complex containing the phebox ligand was achieved by van
Koten [45, 46]. Transmetalation of (phebox)Li with (AuCl)2(dppbp) [31; dppdp
¼ (diphenylphosphino)biphenyl] resulted in the formation of the corresponding
(phebox)Au complexes (32) in high yields (Scheme 11). The Au complexes 32
were found to be good precursors for the preparation of other phebox metal
complexes. In particular, phebox complexes containing early transition metals
were obtained by transmetalation of 32 with metal salts in good yields. In this
reaction, Ti, V, and Cr afforded mononuclear complexes 33, while Zr, Hf, and Nb
gave binuclear complexes 34. These phebox complexes containing early transition
metals served as catalysts for ethylene polymerization. The immobilized (phebox)V
complex on MgCl2-based supports afforded polyethylene with a relatively narrow
molecular weight distribution.
AuCl O
Ph2P
iPr
N
O O
+ Au
Ph2P
N Li N
N O
iPr iPr
iPr
PPh2 2
ClAu
31 32
O C O
(L2)
N N
R2 M R2
R1 (L3) R1
L1
Optically Active Bis(oxazolinyl)phenyl Metal Complexes as Multipotent Catalysts 253
a b c
Cl O O
C C
C C
N N
Ru N N
Ir N O
C Fe
O N
O
O
Cl Br
O O
N N O O
Li
Li N N
N N SnMe3
O O 36
35
The M–C and M–N bond distances are 1.84–2.14 Å and 1.90–2.18 Å, respectively,
and the N–M–N bond angles are 145.7–162.2 (Table 1). The Ni and Fe complexes
have the tendency to have shorter M–C and M–N bond lengths. On the other hand,
early transition metal complexes, such as Ti and V, exhibit longer M–C bond
lengths.
The molecular structures of (phebox)Li 35 and (phebox)SnMe3 36 were also
determined by X-ray analysis (Fig. 5) [47]. The (phebox)Li complex 35 has a dimer
structure, with Li–C bond distances of 2.268(3)–2.299(3) Å. In the (phebox)Sn
complex 36, there is no interaction between the Sn atom and the N atoms. The Sn–C
bond distance of 2.1810(18) Å is longer than those of other transition metal
complexes.
The (phebox)Rh(III) complexes exhibited reactivity for the C–H and C–Cl bond
cleavage of arenes. The reaction of the acetate complex 37 with aromatic
compounds, such as benzene, toluene, chlorobenzene, acetophenone, and anisole,
254 J.-i. Ito and H. Nishiyama
Cl
O O O O O O
X +
N N 120 °C, 50 h N N N N
Rh Rh Rh
80% O O
X Cl
OH2 O O
37 (X = OAc) (X = OAc)
38 (X = Cl) Cl
39a 39b
39a:39b = 1:2.2
tBu tBu
Cl
O O R O O
Cl Cl
N N NH(iPr)2 N N
Rh Rh
80 °C, MS 4Å
Cl
OH2 H2O
40
R
41 (R = H, 90%)
42 (R = Me, 80%)
afforded the corresponding aryl complexes via C–H bond cleavage (Scheme 12)
[48]. For example, C–H bond activation of chlorobenzene resulted in the formation
of the p- and m-substituted chlorophenyl complexes 39a and 39b in the ratio of 1:2.2.
Although there are several mechanisms for C–H bond activation, the reaction with
the Rh acetate complex 37 was proposed as a base promoted C–H bond activation. In
contrast, the chloro analogue 38 did not react with chlorobenzene. This result
supported the premise that the acetate ligand was required for C–H bond cleavage.
The (phebox)Rh complex was also found to undergo oxidative addition to the
C–Cl bond. When the chloro complex 40 was treated with chlorobenzene in the
presence of NH(iPr)2 at 80 C, phenyl complex 41 was obtained in 90 % yield
accompanied by N(¼CMe2)(iPr) [49]. Generally, oxidative addition proceeds via a
Rh(I) intermediate. The inactive (phebox)Rh(III) complex may be reduced by NH
(iPr)2, which serves as a reductant. The preference between C–H and C–Cl bond
cleavage of chlorobenzene can be tuned using different reaction conditions.
The (phebox)Rh complex can undergo a unique C–C bond formation reaction
(Scheme 13) [50]. The reaction of 43 with dichloromethane and diisopropylamine
at 50 C resulted in formation of an azarhodacyclopentene complex 44,
accompanied by a small amount of the diisopropylamine Rh complex 45 in the
ratio of 96:4. This reaction is formally described as a C–C bond formation via C–Cl
bond cleavage of CH2Cl2 and C–H bond activation at the b-carbon of
Optically Active Bis(oxazolinyl)phenyl Metal Complexes as Multipotent Catalysts 255
O O CH2Cl2 O O O O
Cl Cl + Cl
N N N N N N
Rh NH(iPr)2 Rh Rh
Cl
OH 2 iPr N Cl NH2iPr
43 45
44
O O PhCCH O O ECCE O O
AcO
N N N N N N
Rh O Rh O Rh
iPr iPr iPr iPr iPr E iPr
OAc
OH2 O E = CO2Me O
8 46 Ph E
Ph
47
PhCCH
E
E
Ph
48
(phebox-iPr)Rh (8-ip)
(1 mol%)
H2 (1 atm) CO 2Me
Ph H + MeO2C CO 2Me Ph
toluene CO2Me
100 °C, 4 h
48
85%
(Z :E =
98:2)
C
N O
O O CO 2Me O O t Bu H O O
Cl Cl Cl
N N N N tBuOK N N
Rh Rh Rh
Bn Cl Bn Bn Cl Bn Bn Cl Bn
OH2 C O NH
1 N 5S 4R
tBu CO2Me
CO 2Me
49 50
O i Pr
N
AcO H
HO Rh O
4 +
HO CH2Cl2 S
O
40 °C, 24 h N
O iPr
51
44%
O iPr
N
AcO H
4 HO
Rh O (R)-52
+ +
1.1 equiv HO K2CO3 S 50%, 73% ee
O
toluene N
50 °C, 24 h O iPr
r ac -52 53
2.0 equiv 91%
(S )-52
93% ee
Dissociation of the H2O ligand in the (phebox)Rh complex 1 generates a vacant site
on the Rh center, which can accept a Lewis base such as pyridine or acetone.
Complex 1 was used as a traditional Lewis acid catalyst in asymmetric C–C bond
formation reactions. Complex 1 was found to be an efficient catalyst for allylation
of aromatic aldehydes with allyltributyltin, giving the corresponding homoallylic
alcohols in good yields with 61–80 % ee (Scheme 18) [26, 27]. The reaction with
methallyltributyltin furnished the desired products with high enantiomeric excesses
(up to 93 % ee) [54]. Complex 1 also serves as a mild Lewis acid catalyst for
asymmetric hetero Diels–Alder reactions between Danishefsky’s dienes and
glyoxylate derivatives (Scheme 19) [29]. In this reaction, high enantioselectivity
and cis-(endo)-diastereoselectivity were observed. It was proposed that the catalytic
reaction could proceed via a concerted [4 + 2] mechanism rather than the stepwise
Mukaiyama-aldol mechanism. The (phebox)Rh system was also applied to the
asymmetric Michael addition of a-cyanopropionates to acrolein (Scheme 20)
[55]. The (phebox)Rh catalyst was prepared in situ by treatment of [RhCl(coe)2]2
with (phebox)SnMe3 (2). In this catalytic system, (phebox)RhCl(SnMe3) was
considered to be the active Lewis acid catalyst.
258 J.-i. Ito and H. Nishiyama
O phebox Rh (1) OH R2
R2 (5 mol%)
H + SnBu3
CH2Cl2, rt
R1 7 - 12 h R1
MS 4Å
53a: R1 = OMe, R2 = H; 99%, 80% ee (cat. 1-bn)
53b: R1 = H, R2 = Me; 95%, 93% ee (cat. 1-ip)
(phebox)SnMe3 (2-tb)
Me (2 mol%) NC Me
[RhCl(coe)2]2 (1 mol%)
H H
+ NC CO2CHtBu2 CO2CHtBu2
O toluene, 25 °C O
55
82%, 86% ee
O
Rh Rh
O Rh-H O O O OH O
R H
X 1,4-reduction X R H X R X
CH3 CH3 CH3
Rh-enolate
(phebox-Bn)Rh (4-bn)
O O (1 mol%) OH O OH O
(EtO)2MeSiH (1.6 eq) 3S 2R 3R 2R
+ OtBu +
Ph H Ph Ot Bu Ph Ot Bu
toluene, 60 °C, 1 h
then H3O+ Me Me
62 63
98%; anti:syn = 98:2
ant i syn
94% ee (anti); 57% ee (syn)
Ot Bu
Si Me
OO
H
N OH O
R
3S 2R
Rh H Ph OtBu
O N O Si
Me
SiR 3 Ph
R 62
(phebox)Rh
O O (1 mol%) OH O OH O
MePh2SiH
Ph + Ph + Ph
H OtBu toluene OtBu OtBu
Me 50 °C, 0.5 h Me Me Me Me
66 then H3O+ 67 68
r ac, S, R Felkin-Anh anti-Felkin-Anh
+ other diastereomers
(phebox)Rh (4-sb)
O (1 mol%) X O
NaOtBu (5 mol%)
B2pin2 + S
Ph OEt toluene, 80 °C, 0.5 h Ph OEt
86% 73 (X = Bpin)
NaBO 3(H2O) 4
(Phebox)Rh-OR
74 (X = OH) THF/H2O
Ph
B * (97% ee)
III III
(Phebox)Rh B (Phebox)Rh
O O
OR
Ph OEt
4.5 b-Borylation
4.6 Alkynylation
X
O
In this catalytic reaction, both aromatic and aliphatic alkynes could be used. In
particular, the nitro-substituted C1-symmetric Rh complex 4-C1-NO2 showed high
performance in the alkynylation with aliphatic alkynes.
The (phebox)Ru complexes 26 and 28 were found to exhibit catalytic activity in the
asymmetric hydrogenation of simple aromatic ketones in the presence of bases such
as NaOMe and KOtBu (Scheme 33) [40, 41]. While hydrogenation of acetophenone
derivatives showed moderate enantioselectivity (56–65 % ee), higher enantios-
electivity was observed with bulky ketones, such as 2- and 9-anthracenylmethyl
ketones (up to 98 % ee). Transfer hydrogenation of ketones was also catalyzed by
the (phebox)Ru complexes 26 and 28 in the presence of NaOMe at 80 C to give the
S-alcohols (Scheme 34). High enantioselectivity was obtained with bulky ketones.
The formation of the (S)-alcohol in both transfer hydrogenation and hydrogenation
implied that these catalytic reactions involved a similar transition state with a
prochiral face determination.
5.2 Alkynylation
O OH (phebox)Ru
(phebox)Ru (1 mol%)
NaOMe (0.2 eq) 26-ip 99%, 65% ee
+ H2 28-ip 98%, 64% ee
iPrOH, 40 °C, 24 h 28-ph 87%, 56% ee
MeO 30 atm MeO
76
O HO
(phebox)Ru (1 mol%)
NaOMe (0.2 eq)
iPrOH, 80 °C, 24 h
26-ph; 95%, 92% ee
28-ph; 88%, 97% ee
(phebox-Ph)Ru (29-ph)
(12 mol%)
H Ph D Ph
2-propanol-d 8, 60 °C, 3 h
93%
yield (Scheme 36). This result implied the formation of an acetylide intermediate by
the reaction of 29-ph with phenylacetylene.
5.3 Cyclopropanation
(phebox)Ru (27-dph)
(0.5 mol%) 2R 1R 2S 1R
Ph + N2CHCO 2t Bu +
Ph CO2tBu Ph CO2t Bu
CH 2Cl 2, 0 °C, 3 h
78 (trans) 79 (cis)
98% ee 98% ee
90%, tr ans:cis = 92:8
O
O (phebox)Ru (27-dph) H
N2 (1 mol%) O
Ph O
CH2Cl 2, 0 °C, 0.5 h Ph
H
80
96%, 99% ee
Ph
Me O
O O Ph
CNt Bu XN
27-dph Ph CO Ph CO 2tBu
N N Me Ru
Ru C Re
Ph Cl Ph O N X
CNtBu H
Ph Ph
81
X = CO, Cl Ph
Scheme 38 Reaction of the (phebox)Ru complex with isocyanide and a proposed mechanism
(phebox)Pd (18)
CO 2Et (1 mol%) CO2Et
Ph + CH2N2 Ph
CH 2Cl2/CH2Cl2, 0 °C
82
98%
Scheme 39 Cyclopropanation
accepted the carbene ligand. Subsequent direct attack of the alkene to the carbene
produced the cyclopropane with the observed absolute configuration.
(phebox)Pd (20) NC Me
Me (1 mol%)
+ CO 2 Et
O NC CO2 Et toluene O
83
86%, 34% ee
I B(OH)2
(phebox)Pd (17-sb)
Me +
(5 mol%)
S
K3PO4, 50 °C, 24 h Me
84
61%, 49% ee
(phebox)Pt (15-ip)
O
(1 mol%) O N
+
R H NC SO2tol THF, 0 °C, 24 h
R SO 2tol
85
99%, 68% ee (R = Ph)
60%, 75% ee (R = tBu)
Pt(phebox) H
N Ph nBuLi N Ph
Ph Ph
H
-78 °C, CH 2Cl2 nBu
H
86 87
88%, 81% ee
7 Conclusion
The phebox pincer skeleton can readily be introduced into a variety of metal atoms
to form stable NCN-tridentate meridional frameworks having two chiral oxazoline
rings, which confer desirable chiral environments around the metal centers. Chiral
phebox Rh- and Ru-complexes exhibited high catalytic activity as multipotent
catalysts to achieve high enantioselectivity for several types of asymmetric cata-
lytic reactions. The phebox metal complex has the potential to advance the devel-
opment of many organic transformations, such as C–C bond formation and
functionalization reactions.
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Top Organomet Chem (2013) 40: 271–288
DOI: 10.1007/978-3-642-31081-2_9
# Springer-Verlag Berlin Heidelberg 2013
Abstract Amine boranes have received attention as attractive materials for the
chemical storage of hydrogen. Thermal dehydrogenation of these materials is
possible, but catalyzed dehydrogenation would allow for greater control of the
rate and extent of H2 release. Recent work has shown that metal complexes bearing
pincer ligands are competent catalysts for amine borane dehydrogenation.
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
2 Dehydrogenation Studies with (POCOP)Ir(H)2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
2.1 Dehydrogenation of AB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
2.2 Mechanistic Studies of the Dehydrogenation of AB with 1 . . . . . . . . . . . . . . . . . . . . . . . . . 276
2.3 Dehydrogenation of MeAB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
3 Ammonia Borane Dehydrogenation Catalysts Bearing Bifunctional Ligands . . . . . . . . . . . . 278
3.1 Dehydrogenation Studies with (P-N)2RuCl2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
3.2 Mechanistic Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
3.3 Dehydrogenation Studies with (PNP)Ru(H)(PMe3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
4 Nonplatinum Group Metal Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
4.1 Cobalt Complexes Bearing Pincer Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
4.2 Nickel Carbene System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
5 Conclusion and Future Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
Abbreviations
[NH2BH2]5 Pentamer
AB Ammonia borane
BN Boron–nitrogen
COD Cyclooctadiene
DMAB Dimethylamine borane
DOE Department of Energy
ESI-MS Electrospray ionization mass spectroscopy
GPC Gel permeation chromatography
iPr
PN 2-(diisopropylphosphino)ethylamine
IR Infrared
KIE Kinetic isotope effect
KOtBu Potassium t-butoxide
MAS Magic angle spinning
MeAB Methylamine borane
NH2BH2 Amino borane
NMR Nuclear magnetic resonance
PGM Platinum group metal
PNPH HN(CH2CH2PiPr2)2
POCOP 1,3-(OPtBu2)2C6H3
PSiNSiP N(SiMe2CH2PPh2)2
STP Standard temperature and pressure
tBu
PN 2-(ditertbutylphosphino)ethylamine
THF Tetrahydrofuran
wt% Weight percent
XRD X-ray diffraction
1 Introduction
dehydrogenation catalyst [15]. This system utilized the Ir pincer complex (POCOP)
Ir(H)2 (POCOP ¼ [k3-1,3-(OPtBu2)2C6H3]) originally introduced by Brookhart for
dehydrogenation of alkanes [16]. Since then there have been additional reports
describing extremely rapid dehydrogenation of AB by Fagnou [17] and Schneider
[18]. Notably, several of these catalysts employ platinum group metals (PGMs)
bearing pincer ligands.
In recent years, significant attention has turned to the development of non-PGM
catalysts for AB dehydrogenation [19]. For large-scale applications a hydrogen
storage system must employ cheap, widely available materials. Therefore, a practi-
cal catalyst cannot be based on a PGM. To this end we have investigated pincer
complexes of cobalt for application in amine borane dehydrogenation [20].
This chapter describes the current state of AB dehydrogenation catalyzed by
various homogenous metal pincer complexes. Mechanistic studies of the dehydro-
genation reactions and the resulting implications are discussed. Recently, two
reviews summarizing the use of amine boranes [19], and more specifically of AB
[21], for hydrogen storage have appeared.
2.1 Dehydrogenation of AB
Fig. 1 Dehydrogenation of AB with 1 (triangle ¼ 1 mol% catalyst loading, square ¼ 0.5 mol%,
circle ¼ 0.25 mol%)
extended reaction times and/or application of higher temperatures did not lead to
further dehydrogenation activity. The BN products of this MeAB dehydrogenation
reaction were analyzed using Electrospray Ionization Mass Spectrometry (ESI-MS)
and found to be a mixture of cyclic and acyclic oligomers of the form [MeNHBH2]n
(n ¼ 2–20 cyclic) and [MeNH2BH2][MeNHBH2]n[MeNH2] (n ¼ 4–48 acyclic).
Concurrent to this report, Manners and coworkers reported dehydrogenation of
MeAB using the (POCOP)Ir(H)2 catalyst, but with much higher concentrations of
substrate [31]. Under these conditions it was found that polymers were formed
(molecular weight of ca. 160,000 as determined by Gel Permeation Chromatography
(GPC)). In a more recent report, Manners and coworkers extensively studied the
products formed from dehydrogenation reactions of AB with 1 [32].
278 A. St. John et al.
Both the Fagnou and Schneider groups noted that AB is highly polarized and is
more comparable to polar substrates such as alcohols than alkanes [17, 18]. In this
respect, catalysts for the ionic hydrogenation/dehydrogenation of polar bonds (e.g.
C¼O and C–O) may be expected to be more effective for AB dehydrogenation than
those used for olefin hydrogenation/alkane dehydrogenation. Noyori and others
have developed highly effective ruthenium catalysts for the hydrogenation of polar
double bonds [34, 35]. These bifunctional catalysts utilize a nitrogen site in the
ligand backbone to transfer a proton to the ketone or aldehyde oxygen in the
Pincer Complexes as Catalysts for Amine Borane Dehydrogenation 279
Fig. 3 Catalysts 4 and 5 and AB dehydrogenation with pre-catalysts 4 and 5 after activation with
KOtBu
substrate [36]. A similar ionic pathway where the proton is removed from the
nitrogen and a hydride is formally removed from boron was proposed to be
potentially accessible for the dehydrogenation of AB based on the principle of
microscopic reversibility [18].
A survey of known alcohol oxidation/reduction catalysts resulted in the discov-
ery of several precatalysts [17]. The precatalysts were first activated by addition of
KOtBu (3 mol% vs. 0.1 mol% precatalyst) in THF. Subsequent addition of AB to
the activated catalysts resulted in the release of up to one equivalent of H2 at an
enhanced rate as compared to dehydrogenation with 1. The best performing
catalysts (4 and 5) effected the release of a full equivalent of H2 within 5 min at
only 0.1 mol% catalyst loading and at 25 C (Fig. 3). The insoluble product of this
reaction was identified by IR spectroscopy as the same material that was formed
when 1 was used as the catalyst [15]. The catalyst lifetimes were not discussed.
Catalyst 4 was also applied to MeAB dehydrogenation reactions. Using a similar
catalyst activation method as with AB dehydrogenation (KOtBu treatment), these
reactions led to the immediate release of one equivalent of H2. Release of the
second equivalent of H2 occurred at a much slower rate and gave a complex mixture
of soluble products. It is notable that the rate of reaction of MeAB versus AB was
dramatically different for these catalysts, with the first equivalent of hydrogen being
released from MeAB significantly faster. This is in contrast to the observed rates for
the (POCOP)Ir(H)2 system [30], where the dehydrogenation of both AB and MeAB
proceed at a similar rate.
As had been previously explored in the (POCOP)Ir(H)2 system with the goal of
increasing the gravimetric H2 density of the system, mixed AB/MeAB systems
were also examined with precatalyst 4. Addition of 0.1 mol% catalyst 4 to a 1:1
mixture of AB/MeAB resulted in release of roughly 0.8 equivalents of hydrogen.
Surprisingly, the rate of H2 release is decreased compared to reactions with either
AB or MeAB individually. The authors describe these results as preliminary and
280 A. St. John et al.
Concurrent to the report from Fagnou, Schneider and coworkers reported a similar
bifunctional catalyst system [18]. They postulated that the Noyori-style catalysts
utilized for hydrogenation of polar double bonds could be competent for AB
dehydrogenation. Treatment of trans-[RuCl2(PMe3)(PNPH)] (PNPH ¼ HN
(CH2CH2PiPr2)2) (6) with excess KOtBu affords complex 7. Under pressure of
H2, 7 converts to the dihydride complex 8 which cannot be isolated in pure form due
to facile loss of H2 to form the hydride complex 9, which can be isolated in 85 %
overall yield (Scheme 5).
At 0.1 mol% catalyst loading and 25 C, 9 effected the release of one equivalent
of H2 from a THF solution of AB within 4 min. The product was analyzed by
powder diffraction, MAS-11B NMR, and IR spectroscopy. The data suggested the
formation of a polymeric product with general formula [NH2BH2]n [18]. The IR
and powder diffraction spectra of the insoluble BN product do not match that
reported for pentamer [15]. Small amounts of borazine were also detected when
monitoring the reaction via 11B NMR. Borazine production accounts for the slight
excess of H2 over one equivalent observed at higher catalyst loadings.
Measurement of the kinetic isotope effects (KIE) using deuterated AB provided
some insight into the mechanism of these reactions with catalyst 9. Using 0.1 mol%
Pincer Complexes as Catalysts for Amine Borane Dehydrogenation 281
Fig. 4 Calculated reaction pathway for AB dehydrogenation from a model based on complex 4.
Reported values are in kcal mol1
catalyst loadings, KIE values of 2.1 (D3B-NH3), 5.2 (H3B-ND3), and 8.1 (D3B-
ND3) were found. These values are larger than other KIEs reported for AB
dehydrogenation [38]. The KIE data are consistent with a concerted mechanism
where both B–H and N–H bond cleavage occurs in the rate-determining step.
Monitoring the reaction by 31P NMR spectroscopy revealed that amino complex
8 is the predominant Ru-containing species in solution. However, loss of H2 from
complex 8 was observed to be too slow to be a kinetically competent intermediate
in the catalytic cycle.
A later report by Schneider examined the dehydrocoupling of dimethylamine
borane (Me2NHBH3, DMAB) catalyzed by complex 9 [39]. Addition of 9 to a
solution of DMAB results in rapid H2 evolution. Monitoring the volume of evolved
gas revealed two distinct catalytic regimes. At 2 mol% catalyst loading, 9 quickly
dehydrogenates 70 % of the DMAB substrate before slowing, compared to com-
plete conversion of AB at 0.1 mol% catalyst loading. Longer reaction times
eventually lead to quantitative release of one equivalent H2.
Monitoring the dehydrogenation reaction of DMAB by 11B NMR revealed
nearly quantitative conversion to the cyclic dehydrogenation product C (Scheme 6).
An intermediate BN coupled product with linear structure B was also observed.
B was proposed to form via metal-mediated BN coupling (Path 1, Scheme 6). This
is significant because one of the major unanswered mechanistic questions in AB
dehydrogenation concerns BN coupling of dehydrogenated products.
These results show that for DMAB there is evidence for BN coupling occurring
in the coordination sphere of the metal. This BN coupling is in competition with
release of free D which then cyclizes to form C. The authors suggest that the
observed linear BN coupling provides a mechanistic rationale for the formation of
other linear amino borane oligomers [30, 40].
Pincer Complexes as Catalysts for Amine Borane Dehydrogenation 283
Scheme 7 Synthesis of
(POCOP)CoI (10)
While the most active metal catalysts for AB dehydrogenation are pincer
complexes, other reported complexes display promising reactivity. A nickel
carbene-based system reported by Baker yields polyborazylene (Scheme 8) [38].
The extent of H2 release in this system is the highest reported to date (>2.5 equiv.),
although the rate of reaction is slow, requiring a reaction time of 150 min at 60 C.
The initial product of the reaction is borazine which is then cross-linked to form
Pincer Complexes as Catalysts for Amine Borane Dehydrogenation 285
polyborazylene. Mercury poisoning experiments did not affect the rate or extent of
catalytic activity. The KIE data suggests a concerted mechanism for B–H and N–H
bond cleavage in the rate-limiting step.
Discussion of the calculated reaction mechanism is outside of the scope of this
chapter [42, 43]; however, a competition between release of free NH2BH2 and
metal centered BN coupling is suggested. This same competition was implicated in
the DMAB dehydrogenation observed by Schneider [39]. It is interesting to note
that release of NH2BH2 has been suggested as evidence that the catalyst system may
be capable of releasing more than one equivalent of H2 [29]. A recent report by
Conley and Williams employs Shvo’s ruthenium catalyst to rapidly dehydrogenate
AB to borazine [44].
Driven by the need for sustainability, the world energy infrastructure will undergo
significant changes in the coming decades. One key component to the development
of a sustainable energy economy will be finding a suitable energy carrier. Presently,
electrical storage in batteries and high-pressure hydrogen storage are the leading
technologies for “green” vehicles. However, more research is necessary to meet
performance standards expected by consumers have grown to expect.
AB is currently considered a strong contender as a potential material for chemi-
cal hydrogen storage. In recent years, several pincer complexes have been devel-
oped that rapidly dehydrogenate AB to release H2. Further research is needed to
fully understand the mechanism through which H2 is released, but trends are
beginning to emerge already in terms of extent of hydrogen release and the
mechanism of oligomerization of dehydrogenated BN material. Trapping
experiments with cyclohexene have shown that release of NH2BH2 is potentially
an important step in the generation of multiple equivalents of H2 from AB. Experi-
mental and theoretical studies have determined that complexes bearing bifunctional
pincer ligands are especially competent catalysts and this looks to be a promising
strategy for the development of AB dehydrogenation catalysts in the future.
Finally, calorimetric studies have shown that direct regeneration of spent fuel is
not feasible and other indirect methods must be explored. Recently, the regenera-
tion of polyborazylene to AB was reported [33]. Future work will be needed to
continue to develop regeneration pathways.
286 A. St. John et al.
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Top Organomet Chem (2013) 40: 289–318
DOI: 10.1007/978-3-642-31081-2_10
# Springer-Verlag Berlin Heidelberg 2013
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
2 C(sp3)-Based Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
2.1 C(sp3)-Metalated Pincer Complexes Based on All-Aliphatic Scaffolds . . . . . . . . . . . . 291
2.2 C(sp3)-Metalated Pincer Complexes Based
on Non-aliphatic Scaffolds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
1 Introduction
D D
TM TM
D = O, S, N, P or As
D D TM = transition or main group metals
R
R R D
R
D M D M
R
R R D
R
usually planar rarely twisted
PR 2 Y PR2 PR2 PR 2
N PR 2
Y = C, O
PR 2 PR 2 PR2
N N
PR 2
PR2 PR2 R2 P N
R2P R2 P
C(sp3)-based pincer ligands may open new venues in catalysis as well as in many
other research areas where pincer complexes are in use.
Since fundamental and practical aspects of chemistry of the aromatic C(sp2)-based
pincer complexes are well reviewed, in this overview, we wish to concentrate on the
recent developments in the chemistry of PC(sp3)P-metalated pincer compounds.
Although aliphatic pincer complexes have been long overshadowed by the more
robust aromatic ones, several eye-catching C(sp3)-based (almost exclusively, PCP-
type) preligands may be named. For example, alkyl chain [24], cyclohexane [43],
adamantane [44], cycloheptatriene [45], arylmethane [46], diarylmethane [47, 48],
triarylmethane [49], ferrocene [50], and dibenzobarrelene [51] derivatives have
been employed as platforms for the construction of the desired compounds (Fig. 3).
2.1.1 a,v-Diphosphinoalkanes
t t
Bu2 Bu2
P P
H
H H
TM Cl TM Cl
t
P Bu 2 PtBu2
1 TM = Rh 3 TM = Ni
2 TM = Ir 4 TM = Pd
5 TM = Pt
For example, iridium [52], rhodium [53], osmium [54], ruthenium [54, 55], plati-
num [56], palladium [56], and nickel [57] prototypes were synthesized employing
1,5-bis(di-t-butylphosphino)pentane and appropriate metal precursors (Fig. 4). For-
mation of the C(sp3)–metal bond may proceed either via electrophilic activation or
via oxidative addition of low-valent metals across the C–H bond. However, in both
of the cases, yield of the metalated compounds is poor to moderate (depending on
the bulk of the phosphine donors) on account of the formation of large-ring chelates
or linear oligomeric by-products.
t
t t
Bu2 Bu2
t Bu2 P
P Bu2 P P
H TMX n TM
H + ð1Þ
H TM X
t
P Bu 2 P TM P
P tBu2 t t
Bu2
Bu2
Initial comparative IR studies confirmed the expected trans influence of the sp3-
metalated carbon. For example, n (M–Cl) vibrations in 2–5 were found 10–30 cm1
lower than in the analogous aromatic sp2-metalated compounds, suggesting a more
electron-rich character of the metal centers and, consequently, a more reactive
carbon–metal bond [24].
Indeed, its high reactivity has been demonstrated by Zhao, Goldman, and
Hartwig by an unprecedented oxidative addition/reductive elimination equilibrium
displayed in Scheme 1, where the sp3-based Ir(I) complex 6 oxidatively adds across
the N–H bond of ammonia to form the corresponding Ir(III) amido hydride 7 at
room temperature and excellent yield [58]. Remarkably, analogous aromatic pincer
complexes fail to establish the equilibrium favoring the oxidized product. This clear
ligand effect may be attributed to a stronger donating ability of the aliphatic
backbone that enhances electron density at the metal center needed to achieve
activation of otherwise inert ammonia. On the other hand, according to the X-ray
data interpretation, the lone pair of the amido nitrogen is oriented to allow
p-donation into the empty d-orbital that lies in the plane of the iridium(III) centers
containing the ipso carbon. This stabilization is, apparently, less pronounced in the
presence of the conjugated p system of the aromatic PCP ligand, which may explain
the favorable thermodynamics of the reaction. Computational studies have given
support to these findings [59].
PC(sp3)P Transition Metal Pincer Complexes. . . 293
P t Bu2 Pt Bu2
C3 H7 K=9 C3 H7
Ir + NH3 Ir NH2 +
H
Pt Bu2 Pt Bu2
6 7
t
2 BuP H2N
N P t Bu2 NH2 Pt Bu2
N
Ph C3 H7
H Ph Ph H
N Ir Ir Ir N
Ph NH NH
t
2 BuP Pt Bu2 P tBu2
8 6 9
P tBu2 NH2 Pt Bu2 Pt Bu2
N
H H
Ir Ph Ir N Ir N
H -Ph-H NH -H 2 N
Pt Bu2 Pt Bu2 Pt Bu2
10 11 12
Very recent studies by the same group demonstrated similar N–H activation in
hydrazines and hydrozones by 6 (Scheme 2) [60]. In this work, however, the
transformation was not limited to the aliphatic pincer complexes and both 6 and
its aromatic analog 10 were shown to react in a similar fashion, although resulted in
the formation of products of different stability. For example, while 9 is stable at
room temperature, 11 undergoes the second N–H activation at room temperature
over several days to form aminoniterene complex 12 and one equivalent of molec-
ular hydrogen. Here again, structural characterization of the aliphatic complexes
8 and 9 clearly pointed out on the presence of nitrogen-metal p-stabilizing interac-
tion which can rationalize relative stability of the sp3-metalated complexes over the
sp2-based ones.
Carbon dioxide reduction by rhodium [61] and iridium [62] complexes has an
utmost catalytic potential. As was demonstrated, nonclassical dihydrogen complexes
13 and 14 form corresponding formate compounds in the presence of gaseous CO2
(Scheme 3, left). The following sequence of the mechanistic events has been
suggested (1) carbon dioxide coordination to the Z2–H2 binding PCP–Rh center
gives rise to the formation of the dihydrogen complex with a weakly bound
Z1–CO2 complex. This type of Z1 interaction can be viewed as the donation of the
HOMO of the Rh–H2 complex, a dz2 orbital, to the p* orbital of the CO2 molecule;
(2) the dihydride species can undergo the hydride transfer from the Rh center to the C
center of CO2; (3) after the hydride insertion event, the kinetic products formed are
hydridorhodium Z1–formate complexes, which should transform into the most stable
Z2–formate coordination compounds [63].
294 D. Gelman and R. Romm
P t Bu2 Pt Bu2
H -H2 H
Os H Os Cl
H2
Cl
Pt Bu 2 Pt Bu2
21 22
Pt Bu2 Pt Bu2 P tBu2
[RuCl2(cumene)]2 -H 2
Ru Cl Ru Cl
H2
H H
P t Bu2 P tBu2 Pt Bu2
23 24
H 7 (5 mol%) D
C C
R CH2 C6D6, RT R CD2
D0 D0 D 94
t D 97 D 97 H2N D 97 CD2 94
Bu Me3Si
D0 D 97 D 97
(RT, 1 min) (RT, 1 min) (RT, 20 h) (RT, 40 h)
CH3
D 17 D 94 D 0 D 13 O D 96
D
D 97 H3C D 94
NC D 42
D 97 D0 D 44 H3C
D 96
(50 °C, 48 h) (RT, 1.5 h) (RT, 60 h)
conditions and without isomerization of the double bonds [65]. As was demonstrated,
Ir(III) amido hydride complex 7 induces very fast (minutes to hours) room tempera-
ture deuteration of internal and terminal double bonds with absolute regioselectivity
(Fig. 5).
In addition to absolute regioselectivity, the method is highlighted by excellent
functional group compatibility. For example, nitriles, primary amines, alcohols, esters,
and ketones can be present, although acidic a-hydrogens to the electron-withdrawing
groups may suffer from partial exchange. Aliphatic hydrogens do not react under
the developed reaction conditions. This regio- and chemoselectivity allowed effi-
cient isotopic labeling of some biologically active molecules and natural products
(Fig. 6).
Aromatic pincer complexes were found practically inactive under the described
conditions and, therefore, it is suggested the reaction is operated by a mechanism in
which the methine position of the backbone acts as a shuttle. If so, the following
mechanistic scheme may be suggested: after dissociation of olefin, the iridium(I)
296 D. Gelman and R. Romm
D 66
O D
99 OH
OH
O 4 D 91
2 D H
CH(D)3 D D
50
O H
H O
OH O
forksolin altrenogest
(RT, 5 min) (RT, 20 h)
O Pi Pr2
32
(sp3)OP 29 are electrochemically active and undergo facile one electron oxidation
to Ni(III) species. Indeed, chemical oxidation led to the formation of the paramag-
netic 17-electron complexes 30 and 31 (Scheme 7) [67, 68]. Interestingly, attempts
to oxidize the aromatic POC(sp2)OP 32 failed despite that cyclic voltammetry
shows quasi-reversible single-electron oxidation wave (E1/2 ¼ 1.17) [66].
Ni(II) PC(sp3)P 28 (0.5–2 mol%) was found active in catalyzing Kumada
coupling of chlorobenzene with MeMgCl and BuMgCl demonstrating maximal
TON of 84 (Eq. 2) [68]. The same complex serves as a nucleophilic catalyst in
regioselective hydroamination of acrylonitrile with aniline (Eq. 3) [69].
Cl 28 (2 mol%) Me
+ MeMgCl + ð2Þ
THF, reflux
20 h
67% 2%
NH2 28 (1 mol%)
CN
+ C6H5CH3, 60 °C CN ð3Þ
18 h
74%
Cl
29 (0.1 mol%)
+ CCl4 ð4Þ
ACN, 85 °C CCl3
24 h
100%
2.1.2 Diphosphinocycloalkanes
PPh2
Cl PPh2
PPh2 [Rh(COD)Cl]2 PPh2
Rh Vaska
Ph2P PPh2 Ph2 P Cl PPh2
H PPh2 Ir
OC H
34 33 35
M Cl M Cl Pd Cl Rh Cl
H H
Y P tBu2 Pt Bu2 Pt Bu2 Pt Bu2
36: M = Pd, Y = CH2 39: M = Rh 41 42
37: M = Pt,Y = CH2 40: M = Ir
38: M = Pt, Y = O
36
Treatment of 34 with D2 shows H/D exchange at both the hydride ligand and the
methine hydrogen which suggests the lability of the metal–carbon bond (Eq. 5) [61].
P Cl PPh2
D
D2 Rh PPh2
Ph2P
34 D PPh2 Cl PPh2
ð5Þ
Ph2 P
n Ir
34' P H 34'' n
More recently, Wendt [71] and Gusev [72] independently reported on the
employment of cis- and trans-1,3-bis(di-t-butylphosphinomethyl)cyclohexane, as
well as cis-1,3-bis(di-t-butylphosphinito) cyclohexane, as platforms for the con-
struction of palladium, rhodium, platinum, and iridium pincer complexes (Fig. 7).
The chelate systems bearing cis-substituted cyclohexane derivatives adopt a
double-bent conformation with a bisecting perpendicular pseudo-mirror plane
(Fig. 7). For example, five of the atoms in 36 (P1, P2, C2, C7, and C8) are almost
situated in the plane of the complex with the displaced methine groups C1 and C3
pointing away in the same direction. This arrangement results in magnetically
PC(sp3)P Transition Metal Pincer Complexes. . . 299
O Pt Bu2
O Pt Bu2 O P t Bu2
[IrCl(COD)]
toluene Ir Cl
IrCl + 3 H2 H
180 °C H O P tBu2
O P t Bu2 O Pt Bu 2 43
44 was not
observed
different environments above and below the square plane, which is also manifested
in solution with dual resonances in the 13C NMR spectrum of 36 for the tert-butyl
substituents on the phosphorus atoms.
The cyclohexane ring adopts the chair conformation and is aligned with the
plane of the complex, with the equatorial C2–H bond being activated. There is
almost no built-in strain in the cyclohexane ring, which is reflected by its
endocyclic bond angles that do not deviate substantially from free cyclohexane
[40, 73, 74].
Despite that DFT calculations predicted more strain built in complexes bearing
trans-substituted cyclohexane-based ligands (by 9–11 kcal/mol), comparison
between the structural data of 39 and 42 revealed that cyclohexane rings are
practically identical and both adopt almost ideal chair conformation [72].
In contrast to a,o-diphosphinoalkane-based pincer complexes that often experi-
ence temperature induced a- and b-hydride elimination to form isomeric carbene or
olefin-type complexes, cyclohexyl-based PC(sp3)P complexes are thermally stable.
For example, according to TGA, 40 displays a first insignificant weight loss at
220 C in both air and nitrogen, while substantial thermal decomposition starts only
at 250 C in air and 300 C in nitrogen [74]. The thermal stability can be rationalized
by a lesser flexibility of the cyclic ligand frame.
However, interesting aromatization of the cis-1,3-bis(di-t-butylphosphinito)
cyclohexane ligand accompanied by extrusion of three equivalents of dihydrogen
was discovered upon attempted synthesis of the corresponding Ir PC(sp3)P complex
43 (Scheme 9) [74].
Arguably, this unusual transformation may proceed either via iridium-catalyzed
acceptorless dehydrogenation of cyclohexane ligand into the known aromatic
POCOP followed by its facile metalation, or, alternatively, via the formation of
the hypothetical POC(sp3)OP Ir(III) hydride species (43) that undergoes a-elimina-
tion of hydrogen, followed by a,b-hydride shift and double bond isomerization
(Scheme 10). Thus, existence of a- and b-hydride elimination processes cannot be
completely ruled out in the less flexible cyclohexyl-based systems.
Complex 36 was employed as a catalytic promoter in the Suzuki–Miyaura cross-
coupling [75] and Mizoroki–Heck olefination of aryl halides [38, 71]. Although
both these reactions have been shown to proceed under very harsh conditions
(140–160 C), TONs achieved in, e.g., Heck reaction of aryl iodides with activated
substrates were impressive (up to 5.34 105).
300 D. Gelman and R. Romm
Scheme 10 Proposed mecanism for the acceptorless dehydrogenation of the ligand scaffold
PCy2 PCy2
Pd H H2O Pd OH
ð6Þ
H2
PCy2 PCy2
45 46
Yet, catalytic tests proved that palladium chloride bearing the new PC(sp3)P (47)
is a robust catalyst for Suzuki–Miyaura [76] coupling of aryl bromides. This
catalyst operates under much milder reaction conditions and enables quantitative
coupling of a wide variety of electronically activated, deactivated, and/or sterically
hindered, highly functionalized aryl bromides with phenylboronic acid in pure
water with NaOH as base within very short reaction times under low catalyst
loading and without the need for exclusion of air. Hydrophobic substrates, which
lead to inefficient conversions in aqueous medium, were efficiently and quantita-
tively coupled in toluene with K3PO4 as base. Similar reactivity was exhibited by
the same catalyst in Negishi cross-coupling (Scheme 11) [77].
Very often, activity of pincer complexes in cross-coupling chemistry is
contested due to the fact that these compounds cannot participate in the widely
accepted Pd(0)/Pd(II) catalytic cycle and they are only regarded as a source for
palladium nanoparticles that virtually catalyze the reactions [78]. However, based
on the results of the mercury test performed independently by the groups of Frech
[76] and Wendt [75] for the reactions catalyzed by 36 and 47, it was concluded that
the reactions operate either via Pd(II)/Pd(IV) catalytic cycle or via s-bond metathesis
(Scheme 12).
PC(sp3)P Transition Metal Pincer Complexes. . . 301
PCy2
Pd Cl
PCy2
Br Zn 47
46 (0.01 mol%)
NMP, 100 °C R'
R R' 2 30 min
R100 examples
95% yield
O EtO EtO
OEt OEt
S
S
OMe
PCy2
Br
Pd Ph
PCy2 PCy2 Ph
PCy2
Pd Cl PhB(OH)2 Pd Ph Ar-Br
Scheme 12 Proposed mechanism for the suzuki cross coupling of aryl bromides catalyzed by 47
P t Bu2 P tBu2 -
H Cl OTf
TMS-OTf Cl
Ir CO Ir CO
H H
P t Bu2 P tBu2
48 49
P t Bu2 P t Bu2
DBU Ir CO Ir CO
H H
t
P Bu2 P t Bu2
50
P t Bu2 Pt Bu 2 Pt Bu 2
H
Ir CO Ir CO Ir CO
H
P t Bu2 Pt Bu 2 Pt Bu 2
51 52 53
Rh PPh3 Pd TFA Pt Cl
C7
P2
AH1
P3 P1
54
H-SiPh3 CH3-SiPh3
PPh2 PPh2
H-Ph
Rh PPh3 Rh PPh3
PPh2 PPh2
54 CH3-Ph 60
Ph-I CH3-Ph
PPh2 PPh2 H
Ni, Pd, Pt H M
Rh, Fe etc.
PPh2
PPh2
64
P
Cl Cl F
PPh2 PPh2
Pd(COD)Cl2 Ph 2P Pd PPh2 [Ph3 C]PF6 Ph 2P Pd PPh2 6
N N H
N N -Ph3 CH N N
65 66 67
Although it does not fit entirely the definition of pincer complexes, a very elegant
C3-symmetric C(sp3)-metalated ligand developed by Lahuerta, Perez-Prieto, and
306 D. Gelman and R. Romm
Cl H CO
Cl CO
65 Ph2 P Ru PPh2 CO PPh2 Ru PPh2
[RuCl2 (cumene)]2 H
N N N N
68 69
+ anti isomer
N
N PN
Pd P
P
Cl
71
N
N
N P N N PN
H M P
P P P
H
70 P = PPh2 Cl
72 M = Rh
73 M = Ir
P(3)
Cl(1)
P(1)
71
N
74 (1 mol%) TMS
TMS NH P N
80 °C TMS Ir P
P
N
BF4
74 P = PPh2
enantiomers using chiral HPLC was possible. Neither of them was found to
racemize after prolonged heating under reflux in THF solution.
Remarkably, the palladium complex 71 showed very nice activity in Suzuki
coupling of aryl iodides and bromides demonstrating high yields of the cross-
coupled products even with sterically demanding pairs of starting materials
(Eqs. 7 and 8) [49].
Br 71 (0.5 mol%)
(HO)2 B KF, THF reflux
+
24 h
OMe ð7Þ
H3CO
91%
I (HO)2 B 71 (3 mol%)
OCH3 + KF, THF reflux OCH3
24 h ð8Þ
80%
Mechanism of the reaction has not been discussed in detail. However, active
participation of nanoparticles was ruled out based on the results of the mercury test.
In addition, according to the NMR and FAB GC–MS analysis, that showed pres-
ence of the single palladium organometallic species originating from chloride
exchange in 71 by iodide or bromide (in accord with the halide present in the
starting material), and taking into account the unusually crowded arrangement
around the metal center, as well as its 18-electron configuration, s-bond metathesis
rather than Pd(II)/Pd(IV) pathway (Scheme 12) may be hypothesized.
More recently, the same group communicated on application of the square
pyramidal iridium hydride complex 74 (derived from 73/AgBF4) as a catalyst for
stereoselective dimerization of terminal alkynes (Scheme 19) [91].
Dibenzobarrelene-based PC(sp3)P pincer complexes were described by Gelman
and coworkers (Fig. 10, left) [51]. Modularity, rigidity, and three-dimensionality
were the three rationales behind employment of this particular structural motif for
designing pincer compounds. First, unlike many known classes of PC(sp3)P pincer
308 D. Gelman and R. Romm
R R
R R
*
*
M R2P M
R2P PR2 PR'2
IrCl3*H2O
DMFdry
OC
H i Ir
i
2 PrP i
P Pr2
2 PrP Pi Pr2
Cl Cl
75 76
OC
i Ru i Pt
2 PrP Pi Pr2 2 PrP P i Pr2 76
OC Cl Cl
77 78
Scheme 20 Synthesis of the triptycene-based pincer complexes via C–H activation strategy
[IrCl(COE)]2 ClIr(CO)(PPh3 )2
L = PPh3 or
H CH3 CN H
i H i Ir
2 PrP Ir P i Pr2 i
2 PrP i
P Pr2
2 PrP Pi Pr2
L Cl OC Cl
80: L = PPh3 75 79
81: L = CH3CN
LiBEt3 H/H2
81
H
i Ir
2 PrP P i Pr2
Ph 3P H
82
carbon monoxide ligand. Comparison of the iridium–chlorine bond lengths, cis and
trans to C(sp3)–M bond, confirmed a strong trans-influence exerted by the sp3-
carbon, indicating a possible lability of the trans chlorine. However, the most
interesting structural feature of the new compound is an abnormal distortion of
the metalated carbon C1 from its natural tetrahedral geometry. For example, the
C15–C1–Ir angle was found to be 127 (compared to 109 , as is normal for sp3-
hybridized carbon). Remarkably, both octahedral ruthenium (77) and square planar
platinum (78) complexes, synthesized via the same C–H activation approach,
feature similar structural properties. The complexes demonstrate excellent thermal
stability decomposing at temperatures above 260 C and showing no structural
mutations after prolonged heating in DMSO near to its boiling point.
Iridium hydride complexes may be prepared via oxidative addition of low-valent
iridium precursors such as [Ir(COE)Cl]2 or Vaska compound across the methine C–H
bond of 75 giving rise to the formation of 79–81. The 18-electron complex 79 is quite
inert due to the presence of the strongly bound CO ligand trans to the metalated C
(sp3) donor [97], while 80 and 81 bearing more labile ligands can be converted into
dihydride species 82 after treatment with superhydride (Scheme 21) [98].
As mentioned, these strikingly stable organometallic complexes possess a com-
mon structural feature—a strong deviation of the metal–C(sp3) bond from the
geometry characteristic of sp3-hybridized atoms. For example, in the vast majority
of the structurally defined complexes the C–C(sp3)–M bond ranges between 116
and 129 instead of the expected 109 . It has been suggested that this strong
deformation may be reflected in a lability of the carbon–metal bond in the new
three-dimensional PC(sp3)Ps despite the stabilizing “pincer effect.”
To check this hypothesis, possible heterolytic addition of HCl across the
metal–C(sp3) bond in iridium (81) and platinum (78) complexes has been exam-
ined. Theoretical DFT calculations predicted that protonation of 81 by HCl is nearly
310 D. Gelman and R. Romm
C17
C19
C16 C20
C15
C7 C8 C2 C14 C13
C22 C6 C12
H-Cl
C3
C1
C9 C28
C11 ð9Þ
C4
H C5 Cl2 C10
C27
i Ir C21
2 PrP P i Pr2 P1
lr1 C29
C23 P2
MeCN Cl C24 C30 C31
Cl1
81 C25
C26
83 C32
CO2 Me CO2Me
MeO2C
MeO2C
(EtOCH2CH2)2O
reflux
Ph2P TM PPh2 TM
Ph2P PPh2
Cl Cl
84: TM = Pd (71%)
85: TM = Ni (73%)
86: TM = Pt (81%)
O 76 OH
R R i-PrOH, base R R
O
CO CO
CO R
i-PrOH P Ir P
P Ir P
76 base P Ir P
O O Cl
Cl H
Cl
R R
O
OH OH
P Cl
P Cl P Cl P Cl
C Ir Cl
C Ir Cl P C Ir Cl C Ir Cl
H H P P
P H H H H
O Me
Me + +
H H Me R
O O
O Me Me R
Me
P Cl P Cl
C Ir Cl P Cl
C Ir Cl
P P C Ir Cl
H H H H
R P
O O R
R R
H H
O R
R
Product
and the reaction goes to completion even under low catalyst loading conditions at
15 g scale (C/S ¼ 1:100,000).
Based on isotopic labeling tests, it was suggested that the reaction is operated by
the widely accepted monohydride mechanism, although steps such as ketone
insertion into Ir–H bond and displacement of the product from Ir by the
isopropoxide ligand might be greatly facilitated by a strong trans-influence
imposed by the C(sp3) ligand (Scheme 23).
However, another interesting mechanism cannot be completely ruled out, par-
ticularly, on the background of the previously described activation of small
molecules via 1,2-cleavage of the carbon–metal bond in these PC(sp3)P (e.g.,
Eq. 9). Based on this transformation, an alternative mechanistic scheme involving
C(sp3)–metal bond cleavage/regeneration maybe suggested (Scheme 24).
Transfer dehydrogenation of alcohols to form ketones using the same catalytic
system was also demonstrated [102].
Another study performed in the group aimed to demonstrate the advantage of
three-dimensionality and molecular complexity for the design of multifunctional
PC(sp3)P Transition Metal Pincer Complexes. . . 313
02
H OH
H
HO H-H
H
01
Ir
Ph2P PPh 2 O OH Ir1
Cl
87 P1 P2
Cl1
88
catalytic systems [103]. To explore this possibility, iridium hydride pincer complex
87 possessing an acidic sidearm, which is capable of interacting with the catalytic
site, was synthesized (Scheme 25).
The complex 87 was prepared in three stages (1) the quantitative Diels–Alder
cycloaddition of the known 1,8-bis-(diphenylphosphino)anthracene and dimethyl
fumarate; (2) the reduction of the diester adduct; and (3) an essentially quantitative
reaction of the resulting phosphine with [IrCl(COD)]2.
Initial investigation of its properties revealed that 87 is moderately stable in
solution and gradually, but selectively, transforms into a new compound upon
extrusion of molecular hydrogen. Organometallic product of the transformation
was identified as the arm-closed species 88, which features strongly distorted
trigonal bipyramidal geometry around the iridium center (Scheme 25). More
interestingly, addition of isopropyl alcohol to the resulting solution of 88 recovers
the parent 87.
Remarkably, this simple stoichiometric experiment points to a hypothetical
catalytic cycle through which the acceptorless dehydrogenation of alcohols may
proceed (Scheme 26) (a) H2-forming step, leading to the formation of the arm-
closed iridium species 88; (b) ligand exchange step, leading to the arm-open iridium
alkoxide species; and (c) regeneration of the Ir–H catalyst 87 by b-hydride elimi-
nation with subsequent formation of the oxidized product.
Indeed, this transformation was realized under catalytic conditions: 0.1 mol% of
87 in the presence of 5 mol% of Cs2CO3 dehydrogenate secondary alcohols into
ketones in boiling p-xylene over 6 h.
The acceptorless dehydrogenation of primary alcohols and diols could also be
catalyzed using 87, but led to the formation of the corresponding esters and
lactones. Mechanistically, formation of these Tischenko products can be rationalized,
314 D. Gelman and R. Romm
H-H H H
O O
P Ir
a)
Cl P b)
87
H O H
H O
H
O
Ir c)
P P Ir
Cl P P
86 Cl
O
Scheme 26 Proposed catalytic cycle for the acceptorless dehydrogenation of alcohols catalyzed
by 87
OH 87 (0.1 mol%) O
+ H2
R R Cs2CO3 (5 mol%) R R
p-xylene, reflux
OH O R OH OH R O R
87 (0.1 mol%) + H2 + H2
R Cs2CO3 (5 mol%) R R O R O
p-xylene, reflux
3 Conclusion
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PC(sp3)P Transition Metal Pincer Complexes. . . 317
Abstract Pincer complexes have been shown to be widely useful and versatile in
organic synthesis and catalysis, but they have also been employed in a wide range of
intriguing physical and materials applications. The capacity for selective and direc-
tional metal–ligand coordination offers a tool for construction and function. Pincer
complexes have been successfully used as a means for templating macrocycles,
assembling metallodendrimers, functionalizing surfaces, and functionalizing polymer
chains. Furthermore, pincer complexes have proven to be useful mechanistic probes
of polymer physical processes, linear polymers, networks, cross-linked brushes,
films, and gels. Recently, the activity of pincer complexes has extended into the
realm of mechanochemistry, with applications in fundamental mechanistic studies as
well as mechanocatalysis. This chapter explores the use of pincer metal–ligand
coordination events in these various physical and materials contexts.
Contents
1 Pincer–Ligand Coordination as a Materials Construction Tool . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
1.1 Building Metallodendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
1.2 Building Films and Surface Patterns with Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . 325
1.3 Functionalizing Existing Polymer Chains . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
1.4 Metallodendrimers as Templates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
Fig. 2 Cartoon
representation of a self-
assembled metallodendrimer
built out to the second level.
Curved wedges and balls
represent pincer complexes
and coordinating ligands,
respectively
The first example of pincer complexes being used to build dendritic nanospheres
with well-controlled size distribution was demonstrated in 1995 by Huck et al. [14].
The core structure was a traditional tridentate pincer complex coordinated to the
nitrile of an organic ligand. The coordination geometry of nitriles and similar
ligands to the pincer PdII center is that of a square planar complex. The smallest
unit (monomer) of a repeating dendritic structure was constructed by including
three coordinations–ready prongs: two pincer complexes and one cyanomethyl
group (Fig. 1).
When a solution of the repeat unit 1, Fig. 1, is heated in nitromethane, the
coordinating solvent molecules (acetonitrile) evaporate and the cyanomethyl group
from a separate unit is replaced as the fourth coordinating ligand around one of the
PdII centers. This coordination of the nitrile from one monomeric unit to the pincer
motif of another results in a continuous branching pattern, shown out to the second
level in Fig. 2.
The coordination can be followed using FT-IR spectroscopy to monitor the shift
in the characteristic peak of the CN bond; the uncoordinated nitrile stretch at
Physical and Materials Applications of Pincer Complexes 323
2,250 cm1 shifts to a value of 2,290 cm1 upon coordination [14]. The addition of
small amounts of acetonitrile breaks the dendrimers apart and regenerates the
original monomer. This result highlights how the spheres retain the reversibility
of the pincer complex, in contrast to the irreversible nature of covalent bonds. As
with other supramolecular interactions, reversibility of this sort is one of the main
advantages achieved when using pincer complexes as a construction tool. Revers-
ibility provides both advantages in synthesis (error correction) and performance
(e.g., stimulus response) that might be useful for certain applications.
Further characterization allowed the size and shape of the presumed dendritic
assemblies to be determined. Quasi-elastic light scattering (QELS) indicated that
the hydrodynamic diameter of the assemblies in solution is 200 nm [14]. In
addition, the assemblies were deposited onto surfaces and characterized by atomic
force microscopy (AFM) in the solid state; the diameter of the spheres measured by
AFM on the surfaces was on average 205 nm, in excellent agreement with the
solution measurements. Both gold and glass surfaces were employed in the AFM
experiments to show that the material of the surface did not dictate the size or shape
of the assemblies. Lastly, transmission electron microscopy (TEM) was used to
determine the size of the globular structures that resulted after the evaporation of
the solution on a carbon-coated copper grid. The TEM results gave diameters in the
range of 150–200 nm, a value that is consistent with both the QELS and AFM data.
Branching was shown to be essential to the building of these spheres; when
nonbranched complexes of similar composition were exposed to the same assembly
conditions, no globular structures were observed by TEM [14].
The initial work described above demonstrated that pincer complexes are useful
building blocks for the divergent construction of dendritic nanospheres, proving a
new construction motif and concept for the synthesis of dendritic architectures. The
relative ease of construction and multiple handles for structural variation on the
molecular level suggested that pincer complexes might be used to produce more
complicated and intricately designed structures. Further studies, described below,
determined what factors influenced this method of construction and what
limitations are inherent to the methodology.
In later work, Huck et al. [2, 3] showed that they could extend the concepts
developed in the first metallodendrimer system to build larger systems with the
same repeating unit. They were also able to investigate what variables dictated the
size of these branching structures. A modified approach was taken, built upon a
similar but slightly modified repeat unit. Unlike the first system, composed of only
the repeating unit, the metallodendrimer synthesis was initiated from a core unit
that remains at the center of the dendrimer throughout its synthesis.
This core unit is similar in structure to the repeat unit 1 utilized above, but it has
three pincer PdII complexes instead of two. The pincer complexes are initially
protected with a chloride ligand, as chloride is not displaced by nitrile and it
therefore prevents coordination by cyano groups from the other monomers.
324 J.L. Hawk and S.L. Craig
Fig. 3 Representation of the core unit (a) and the first layer of the divergent dendrimer (b) built
with a branched pincer structure. The chloride ions act as a protecting group that inhibits undesired
coordination. Curved wedges represent the pincer moieties
Several common characteristics are seen in the dendritic systems, including that
they meet the obvious requirement that each individual building block or repeating
unit must contain all of the necessary information for complete self-assembly (i.e.,
both the pincer and the ligand) [17]. The orientation and components of these units
can be varied, but they must be able to form the branched structures without
additional materials or outside intervention. By building the individual units to
contain all the necessary information, the ultimate assembly process is simplified
and allows for structures to form quickly and easily.
Physical and Materials Applications of Pincer Complexes 325
Because pincer coordination complexes can be quite strong, easy to work with, and
maintain the reversible nature desired for construction, they offer an intriguing
combination of potential uses within the materials arena. They offer a useful
method for the physical construction of systems that have mechanical integrity,
so that ultimately they might be developed into useful materials. The structural
integrity of pincer-based metallodendrimers, for example, allows them to be spin-
cast from solution to form molecularly thin films, which offer a wide variety of
potential applications in material science [13]. Metallodendrimers of the fifth
generation (Fig. 3) generated films of ~4 nm thickness as characterized by AFM
and TEM (Fig. 4).
Another application of pincer-based assembly is found in surface patterning, for
which existing techniques are often time consuming and costly. Developing a fast
and simple method for functional surface patterning is an ongoing goal in the field of
nanoscience. Metallodendrimers were linked to a surface by modifying them with
long sulfide chains for attachment to gold surfaces [12]. These dendrimer tethers can
then be inserted into a self-assembled monolayer on a gold surface at defect sites
(essentially holes in the monolayer) that form during monolayer self-assembly. The
dendrimer attachment pattern can be characterized using AFM [12]. The overall
density and positions of the dendrimers are controlled using different techniques for
the monolayer. Direct positioning of pendant groups using pincer complex affinity
was posited to be useful for future surface patterning techniques [12].
In addition to serving as a critical structural unit in metallodendrimers for film
and surface pattern fabrication, pincer complexes have also been employed as the
primary structural “glue” for multilayer film deposition. The so-called Coordination
Polymer Multilayer (CoPM) technique features polymer chains with pincer units
incorporated along the backbone [22]. The CoPM strategy is shown in Fig. 5.
326 J.L. Hawk and S.L. Craig
The pincer complex is linked via a tether to the backbone of a polymer synthesized
by ring-opening metathesis polymerization (ROMP). The coordinating pyridine
ligand is displayed as a side chain functionality on the second polymeric compo-
nent, poly(vinyl pyridine) (PVP). CoPMs are synthesized by the alternating depo-
sition of these two complementary polymeric components, in a process inspired by
electrostatic layer-by-layer deposition. The ability to construct the CoPMs arises
directly from the PdII pincer’s responsiveness, inertness towards unwanted
functionalities, and specific strength of coordination towards pyridine, in addition
to its chemical compatibility with the ROMP conditions. The CoPMs are compara-
ble in strength, durability, and stability to their covalent multilayer counterparts.
Interestingly however, the CoPMs exhibit many responsive behaviors that are
similar to polyelectrolyte multilayers, whose durability is not as great [22].
In contrast to building multilayers from polymer chains with the pincer
monomers in the backbone, small molecule pincer complexes have also been
used to cross-link layers of PVP chains [8]. The combination of PVP and pincer
cross-linkers produces uniform films in nonaqueous environments. The structure
and properties of these films can easily be modified by changing the solution
concentrations and molecular weight of the PVP chains, adding competing ligands,
or changing the pH. Figure 6 shows how different layers of polymers can be brought
together by the coordination of the free small molecule, bis-pincer complex. Both
types of multilayers offer interesting potential for building films of different desired
properties [8].
Physical and Materials Applications of Pincer Complexes 327
Fig. 5 Representation of coordination polymer multilayer (CoPM) buildup on gold, showing the
pincer–ligand coordination responsible for building the layers. Reproduced from [22] with per-
mission from Copyright # 2008 John Wiley and Sons
N BF4–
+
PhS Pd SPh
PhS Pd SPh
+
N BF –4
Fig. 6 Representation of separate PVP layers being brought together with the small molecule bis-
pincer complexes. Reproduced from [8] with permission from Copyright # 2008 American
Chemical Society
There is a growing desire within the field of polymer chemistry for fast synthesis
and easy post-synthetic polymer modification. Often, traditional methods of syn-
thesis and additional side chain modifications rely on covalent chemistry. These
reactions often require extensive steps and subsequent purification. If the reactions
are not quantitative, unwanted side reactions and other modifications can take place
along the polymer chain. The use of non-covalent chemistry has recently gained
popularity for its ability to offer selectivity in associations as well as simplicity as a
328 J.L. Hawk and S.L. Craig
The first use of pincer complexes as a tool for post-synthetic polymer modification
was reported by Pollino et al. [1]. In order to take advantage of pincer coordination
in this context, it is important to identify with what specificity the coordination
events take place and what types of modifications can be made. Initially, Pollino
et al. constructed random copolymers within which to demonstrate the viability of
the approach and to characterize this method of functionalization [1]. Random
copolymers were built with two different side chain functionalities: PdII pincer
units and units capable of hydrogen bonding. The complementary partners for the
pincer complexes were a range of pyridine ligands, while the hydrogen bonding
units on the polymer had a separate partner motif with which to associate. The
orthogonality of the pincer–pyridine coordination and the hydrogen bonding
offered the chance for rapid and specific multifunctionalization. As noted in
previous sections, pincer-PdII–pyridine coordination is characteristically reversible,
spontaneous, simple and self-repairing (in that an undesired association tends to
reverse quickly and give way to a desirable association event) in nature, and the
system’s potential to self-correct in this way was important in the context of the
desired application, which involved two distinct but simultaneous non-covalent
functionalization events. To better determine if the pyridine–pincer interactions
were truly orthogonal to the hydrogen bonding interactions, a set of three different
methodologies was employed [1].
This first methodology successfully showed that the pincer metal–ligand inter-
action is both selective and spontaneous. The pyridine ligand was added to the
copolymer solution, and the pyridine ligand could only be observed to associate
with the desired pincer complex, and not the hydrogen bonding unit. The second
methodology revealed that a stepwise multifunctionalization was possible. The
pyridine and hydrogen bonding ligands were added sequentially. The same final
functionalized state was achieved regardless of the order of addition, and the extent
of pyridine coordination matched that obtained in the absence of the hydrogen
bonding unit. Finally, the authors reported that the same final state was obtained
again if both types of ligands were added at the same time. Not only was the final
state the same, but the rate of formation did not change as a function of order of
addition. This combination of studies, shown schematically in Fig. 7, demonstrated
Physical and Materials Applications of Pincer Complexes 329
Hydrogen- Metal-
Bonding Coordination
One-Step
Orthogonal
Self-Assembly
Metal- Hydrogen-
Coordination Bonding
Et
O Ph BF4– Ph BF4–
N H O S S
N H N Pd N Pd N C
N
N H O S S
O
Ph Ph
Et
2 3 4
Fig. 8 The three different self-assembly motifs used in the study of post-synthetic polymerization
multifunctionalization: (2) three-point hydrogen bonds, (3) pincer complex coordinated to pyri-
dine, and (4) pincer complex coordinated to nitrile. Reproduced from [4] with permission from
Copyright # 2006 American Chemical Society
Fig. 9 A representation of the two different combinations of recognition units: (a) a block
copolymer backbone containing the pincer units as the recognition units and (b) a block copolymer
backbone containing the ligands as the recognition units. Reproduced from [4] with permission
from Copyright # 2006 American Chemical Society
architectures of two blocks. Overall, the order and compositions of the blocks do
not influence the coordination events between the pincer complexes and their
complementary ligands [4].
The initial state (bound to polymer vs. free in solution) of the ligand and metal
did not influence the self-assembly (Fig. 9), and orthogonality vs. hydrogen bond-
ing was preserved in the reversed coordination cases.
Of course, the ultimate goal in functionalizing either block or random copolymers
is to modify the properties. There were two observed changes in the thermal
Physical and Materials Applications of Pincer Complexes 331
properties of these polymers. First, metal coordination leads to a decrease in the glass
transition temperature of the polymer, an observation the investigators attributed to
the disruption in the original intermolecular forces between polymer chains. Second,
the thermal stability drops when the polymers are coordinated to the ligands. Further
work is necessary to accurately relate these changes in properties to the various
structural changes that accompany functionalization, a general concern for polymer
property prediction as increasingly complex functional groups are used more and
more frequently in polymer science [4].
More complex polymer structures were built using two different hydrogen bonding
motifs in addition to the pincer complex [24]. Similar to the early systems, the
functionalization behavior of these polymers was once again studied. As before, the
presence of additional functional groups caused no observed change in the associa-
tion constants of any of the individual coordination sites. The pincer groups were
shown to coordinate rapidly and reversibly to the ligands, and functionalization was
achieved without the need for subsequent purification. The multiple coordination
events occurred independently of each other, and the order in which they were
added did not influence their properties; pincer–ligand coordination was not
disrupted by the hydrogen bonding groups, nor did it disrupt the association of
those motifs [24].
To probe the physical properties of these modified terpolymers, a solvent study
was carried out [25]. It was observed that by changing the solvent, one coordinating
group could be selectively removed from the chain, with the addition of another
coordinating ligand. These induced disassembly events can ultimately lead to
tunable control over the polymer’s properties. All previous studies carried out in
halogenated solvents showed that the three coordination events were orthogonal,
but when the solvent is changed to a chloroform/dioxane mixture, the hydrogen
bonding is disrupted by the addition of the ligand that can coordinate with the
pincer complexes. It was determined that the dioxane competes with and ultimately
decreases the strength of the hydrogen bonding events. The pincer–ligand interac-
tion, however, is robust in all solvents and is not susceptible to solvent disruptions.
It was further determined that the presence of free silver ions from the pyridine-
pincer–ligand exchange disrupts the hydrogen bonding. This disruption is not
dependent on the anion of the silver salt or the solvent that the silver salt is added
with. This same disassembly can also be triggered by changing the polarity of the
solvent [25]. The pincer complexes offer a robust method of modifying polymer
chains and ultimately changing the physical properties of these systems.
Although the focus of this chapter is on the use of pincer complexes in materials-
related physical applications, we point out that pincer coordination can also provide
332 J.L. Hawk and S.L. Craig
Y N Y
Me2N Pt NMe2
Cl
Me2N Pt NMe2
Me2N NMe2
Y Y
Me2N NMe2 Pt Pt
N N
Y N Y Pt Pt N N
Cl Cl Y Me2 Me2 Y
N N
Me2 Me2
5a: Y= O 6 3 BF4
5b: Y= CH2O
Fig. 10 Structures used in template directed synthesis: (5) pyridines bearing long alkyl chains
with terminal olefins, (6) core template that is shape persistent and contains multiple pincer
complexes available for coordination to the pyridine, and (7) coordinated template to olefin
containing chains, ready for ring formation. Reproduced from [28] with permission from Copy-
right # 2003 John Wiley and Sons
a valuable tool for templated synthesis. The selectivity, orthogonality, and direc-
tionality of pincer coordination work to great advantage in this context, because
reactants can be preorganized through coordination around a template and subse-
quently reacted to give a final molecular structure that is otherwise difficult to
obtain. An elegant and useful example of the templating approach is found in the
synthesis of macrocycles.
The core templates in this approach, developed by van Koten and coworkers
[26–28], are shape persistent metallic units containing multiple of pincer complexes
(Fig. 10). Pyridines bearing long alkyl chains with terminal olefins (5a and 5b)
coordinated to the displayed pincer complexes (6), with the idea that the olefins
could be joined through metathesis to form large macrocycles. It was observed that
the template unit did coordinate to the pyridine containing chain quantitatively (7),
setting the stage for subsequent ring formation.
Olefin-substituted chains of different lengths were studied to see if there was a
specific length needed to enable full macrocyclization [26]. Depending on the olefin
chain used, the isolated yield of the desired macrocycle ranged from 0 to 70 %. A
minimum chain length of 11 atoms in each of the two branches on each of the three
pyridine ligands was required for macrocyclization, leading to monodisperse
macrocycles of over 60 bonds along their perimeters. Once the macrocycles were
formed, the template could be removed easily with the addition of aqueous sodium
chloride. These pyridine-functionalized macrocycles could then be further modified
and used as components in reversible host/guest systems. Because a variety of
shape-persistent templates can be prepared, including a hexametallic species [29],
the strategy is potential suitable for a range of targets.
Physical and Materials Applications of Pincer Complexes 333
Fig. 11 (a) Several different pincer complexes used in kinetic studies with different metals and R
groups and (b) various pyridine derived ligands which can coordinate to the different pincer
complexes
however, that of 8a•9 shows broad peaks that are indicative of exchange near the
NMR timescale. Heating the NMR sample to only 30 C leads to coalescence of the
peaks and corresponds to an exchange rate of 100 s1 at that temperature. In
contrast, the same peaks in 8b•9 remain separated until 90 C, above which the
reduced concentration of bound ligand makes coalescence impossible to identify
clearly. The orthogonal control of dissociation dynamics relative to complexation
thermodynamics can be viewed as a “macromolecular analog of the kinetic isotope
effect,” and its use in a variety of mechanistic physical studies is the focus of this
section [5].
We have previously discussed how covalent polymer chains can be modified non-
covalently by using side chain pincer coordination, but similar pincer associations
are also useful for building the main chain structure by attaching the pincer
complexes and ligands to the ends of difunctional polymers and small molecules
[5]. The metal–ligand associations between chain ends lead to longer, reversible
polymer chains. A specific example is shown in Fig. 12. Mixing a solution of bis-
Physical and Materials Applications of Pincer Complexes 335
Fig. 12 Example of pincer coordinations to form supramolecular polymer chains with 10a or 10b.
Reproduced from [5] with permission from Copyright # 2003 American Chemical Society
Not only can pincer complexes be incorporated into polymer backbones to induce
physical changes, but the bis-pincer small molecules can be used to cross-link
polymer chains to form reversible networks [6]. When the bis-pincer complexes
are added to solutions of PVP, the multiple pincer–pyridine coordination events act
as cross-linkers, leading to the formation of reversible networks (Fig. 13) [6]. These
systems provide excellent model systems for exploring the fundamental behavior of
supramolecular polymer networks in general.
The network physical properties were monitored as the small molecule pincer
cross-linkers were added to the PVP solutions [10]. As the concentration of cross-
linkers went up, there was a concomitant increase in the sample viscosity,
indicating the formation of reversible networks. The viscosity increase is reversed
upon the addition of dimethylaminopyridine (DMAP), which outcompetes the
pyridine side chains for the pincer complexes and disrupts the cross-linking.
Furthermore, the addition of a mono-functional, rather than a bis-functional pincer
complex to solutions of PVP leads to no observed increase in viscosity. Clearly, the
bis-functionality of the pincer complexes, and the associated cross-linking, is
responsible for the changes in the physical properties. Figure 14 shows the relation-
ship between viscosity and the cross-linkers added (10a and 10b).
While the pincer complexes are useful for forming the reversible networks, it is
important to study the influence of the kinetics and thermodynamics of the system
as well. As demonstrated with the main chain studies, kdiss is important in defining
many of the physical properties. When pincer complexes of slightly different
chemical structures were compared, a drastic difference in properties was observed.
The resulting viscosities of the different networks scale with the kdiss of the specific
pincer complex used. When comparing two systems with nearly identical values of
Keq but significantly different values for kdiss, the viscosities are still drastically
different. This indicates that it is the lifetime of the cross-links that ultimately
dictate the viscosity of the solution and not the strength of the interaction.
Changing the steric bulk of the pincer complex influences the kinetics of the
interaction, but the thermodynamics of the interaction can be controlled with the
metal in the complex. By changing the PdII to PtII the thermodynamic strength of
the interaction increases even. When different pincer complexes with different Keq
values were used, however, the mechanical response still scaled with the kdiss.
When the entire family of cross-linkers was compared (kdiss ranging from
0.0006 s1 to 1,450 s1) all relative viscosities scaled with the kdiss and not Keq.
Clearly, the chemical structure of these pincer complexes dictates the properties
and physical functions of these reversible networks [10].
Within this family of pincer-based networks, the role of reversible molecular
dynamics on material response was explored through the steric effects in the pincer
Physical and Materials Applications of Pincer Complexes 337
–OTf
R2N
+ H –OTf
N M N NR2
H +
R2N O N M N
O NR2
alkylamino ligands, both within the Pd complexes 10a–b and the slower, more
strongly coordinating Pt complexes 10c–d. As with the linear polymers, the inde-
pendent control of kinetics is effective and particularly useful; cross-linkers 10a
and 10b are structurally identical components within the network, and so their
similar thermodynamics (Keq ¼ ~30 M1 for 8a•9 and 8b•9) ensure that the extent
and nature of cross-linking are essentially the same in the two samples (or between Pt
(II) pincer molecules 10c–d; where Keq ¼ 8 103 M1 for 8c●9 and 4 103 M1
for 8d●9).
Above a critical concentration of cross-linkers, the absolute and relative
behaviors of the various networks are quite different, both qualitatively and quanti-
tatively. As seen in Fig. 14, the viscosity increases by up to several orders of
magnitude over a relatively narrow range of cross-linking content, and past this
transition the materials behave like weak gels. This change in properties is
attributed to a sol-to-gel transition, and once the macroscopic network is formed,
the macroscopic mechanical response of the gel requires that the cross-links
dissociate.
The central role of cross-link dissociation is seen in the relative viscosities at
cross-linker concentrations beyond the sol–gel transition. In this regime, the
338 J.L. Hawk and S.L. Craig
relative viscosities of the samples are proportional to the lifetime (t ¼ 1/kd) of the
coordinative metal–pyridine bonds that define the cross-links [10, 53]; for example,
the zero shear viscosity of 100 mg mL1 10a•PVP is a factor of 80 less than that of
the isostructural network 10b•PVP (Fig. 13). The difference of a factor of ~80 in the
network viscosities is within experimental error of the difference in the ligand
exchange rates, and a full spectrum of dynamic mechanical behavior is similarly
well correlated. The frequency-dependent storage and loss moduli, G0 and G00 , for
networks of either 10a•PVP or the related 10b•PVP, are reduced to a single master
plot when scaled by the corresponding ligand exchange rates, measured on model
systems [10]. In other words, the full range of physical mechanical behavior of the
networks can be tied back to a single-molecular event, the dissociation of a pyridine
ligand from a pincer complex. The same relationship is valid for both the Pd (e.g.,
10a/b) and Pt (10c/d) cross-linkers, even though the equilibrium association
constants for the Pt complexes are roughly a factor of 102 higher than those of
the corresponding Pd complexes.
Polymer networks formed via weak associations often have quite rich behavior
under shear. Depending on the specific system and its environment, networks might
grow less viscous once forced to flow (shear thinning, the most common example of
which is found in striking a bottle of ketchup to get its contents to flow more easily),
or they might become more viscous under induced flow (shear thickening, observed
in quicksand and in concentrated cornstarch–water suspensions). Such responses
are classified as “nonlinear rheology,” and the important point for purposes of this
chapter is that the molecular mechanisms that dictate the various responses are
often unclear. The kinetic control afforded by the pincer complexes has proven to
be quite useful in establishing the details of these processes, and in fact have
uncovered hidden and unanticipated polymer physics.
The nonlinear rheological properties of the pincer–PVP networks depend on the
concentration of the PVP. When the networks are formed from less concentrated
solutions of PVP (specifically, at concentrations in which the polymer chains are
not entangled with each other), the application of shear above a critical shear rate
Physical and Materials Applications of Pincer Complexes 339
leads to shear thickening [54]. As with the linear rheology, a change in cross-link
dissociation rate provides immediate insight into the phenomenon, because the
shear rate at which the shear thickening begins is proportional to the stress-free
lifetime of the pincer–pyridine bond. The onset and magnitude of the shear
thickening depend on the amount of cross-linkers added, and further experimental
work has identified the primary mechanism of shear thickening to the shear-induced
transformation of intramolecular cross-linking to intermolecular cross-linking, as
shown in Fig. 15.
The story changes somewhat when the concentration of the PVP is higher, so
that the PVP polymer chains are wrapped around each other in addition to being
bound to each through the pincer complexes. The kinetic control of pincer–pyridine
dissociation becomes especially useful in this complex environment. Under steady
shear, however, the scaling relationships in the semidilute unentangled regime
break down dramatically. This breakdown is not only in the quantitative scaling
behavior, but even in the qualitative shear response of different systems: shear
thinning is generally observed for samples with cross-linkers that have a faster
dissociation rate (e.g., 12a), while shear thickening is still observed for cross-
linkers that have a slower dissociation rate (e.g., 12b). Clearly, the picture is
much more complicated than that of the systems with lower concentrations of
PVP. In addition, the change in fundamental mechanism was not predicted by
any existing theories of shear thinning and shear thickening, and it is difficult to
imagine how the effect of cross-linker dynamics might have been observed without
the ability to vary the kinetics in otherwise identical systems that is afforded
through the pincer complexes [55]. Further mechanistic work suggested that two
critical processes compete in the time after a cross-linker dissociates: the cross-
linker tries to re-associate, and at the same time the now freed polymer chain
segment tries to orient in a way that would permit additional intermolecular
cross-linkers to form. When cross-linker re-association is rapid, the polymer does
not have time to orient for new cross-link formation under the shear flow and shear
thinning, rather than shear thickening, results [56].
The pincer complexes have also been used to shed light on how more complex
material mechanical properties might be programmed via a combination of multiple
supramolecular interactions. Pincer–PVP networks were formed similarly to the
340 J.L. Hawk and S.L. Craig
Fig. 16 Storage modulus, G0 , vs. frequency for (red filled diamond) 2.5 % þ 2.5 % (12b þ 12c)
•PVP, (open square) 2.5 % 12c•PVP, (open traingle) 5 % 12c•PVP, (open circle) 2.5 % 12b•PVP,
and (open diamond) 5 % 12b•PVP. All networks 10 % by total weight in DMSO, 20 C.
Reproduced from [57] with permission from Copyright # 2005 American Chemical Society
1000000
~x 3.3
10000
Viscosity (Pa s)
3.2
100 ~x
1
3.1
~x
0.01
0.1 1 10
% Cross-linker
Fig. 17 The effect of cross-linking percentage on viscosity of transient networks formed from
PVP with pincer complexes: 12a●PVP (filled diamond), 12b●PVP (filled circle), and 12c●PVP
(filled triangle). Reproduced from [53] with permission from Copyright # 2007 Royal Society of
Chemistry
10000
1000
Viscosity (Pa s)
100
10
0.1
0.01
(a) (b) (c) (d) (e) (f)
Fig. 19 Storage modulus as measured by the oscillatory rheology of covalent and hybrid DMSO
gels: “pure” covalent gel (multiplication symbol); gel•12a (filled circle); gel•12b (filled triangle);
gel•12c (open triangle); and gel•12d (open circle). Reproduced from [9] with permission from
Copyright # 2006 The Royal Society
structural similarity of the related pincer complexes and their comparable pyridine
coordination thermodynamics ensures that the equilibrium structures of the two
gels are effectively identical. The timescales at which the various cross-linkers
begin to contribute to material mechanical properties, however, are not identical,
but instead reflect the intrinsic dissociation rates of the various pincer complexes. In
the hybrid systems, as in the mixed reversible-only systems, the individual supra-
molecular cross-links bear stress and act as largely independent contributors to the
dynamic mechanical properties.
Looking ahead, these and related hybrid networks offer the opportunity for future
mechanistic studies of important, but complex, processes whose mechanistic origins
are still poorly understood, including: gel fracture [61], self-repair [62], and energy
dissipation [63]. Studies in these areas would follow cleanly from the structure–-
activity studies described above, and should benefit from the groundwork laid by the
prior efforts. The shear thinning and shear thickening behavior described in earlier
sections shows how pincer complexes can be used as effective probes of highly
complex responses for which conclusive molecular interpretations are often not
available.
and pincer complexes have played a central role in at least two important advances
within the field. They have been used (1) to demonstrate fundamental principles of
mechanochemical activation and (2) as an early example for the mechanore-
sponsive catalysts.
Given the central role of the pincers in storing and responding to an applied
mechanical stress in the networks, it is reasonable to speculate on the effect of
that stored mechanical stress on the cross-linker dissociation. This question of how
a force of tension within a polymer affects the rates of bond dissociation processes,
although considered in various contexts over the years [64], had not been quantified
experimentally for systems other than homolytic bond scission until 2006, when it
was approached in the specific context of pincer–pyridine complexes. The force-
induced displacement of pyridine by dimethylsulfoxide (DMSO) was examined
experimentally using single-molecule force spectroscopy by Kersey et al. [51].
Briefly, the tip of an atomic force microscope was used to pull one end of a polymer
away from a surface to which the other end of the polymer was attached. A pair of
pincer–pyridine coordinative bonds in the center of the polymer provided a spot for
dissociation that could be characterized as a function of force. The AFM experi-
ment is a kinetic measurement; the experiment probes the probability that the bond
breaks as opposed to remaining intact under an applied load across a given time
interval. A load is applied, and the mechanical energy is stored in the intact,
elongated polymer until the metal–ligand bond breaks, at which point the energy
is dissipated. The energy is stored in the elastic deformation of the polymer coupled
to the deflected AFM tip, and so the release of the tip signals the breaking of the
metal–ligand bond.
Several insights were established from investigations of the mechanics of ligand
exchange in pincer complexes. A first general conclusion from the AFM studies is
that, as might be expected, the rate of ligand dissociation increases as the force
applied to the ligand increases. Second, as shown in Fig. 20, the probability of
complex survival depends on the rate at which the force is loaded into the bond
normalized by the stress-free lifetime of the bonds—scaling behavior that is
strongly reminiscent of the mechanical behavior of the macroscopic networks.
From a materials perspective, then, any contributions from force-induced rupture
to the network mechanical response are likely to fall neatly within the same scaling
behaviors reported earlier. Third, the nature of the force–rate relationship strongly
suggests that the mechanism of ligand displacement under mechanical load is not
greatly distorted from that of the force-free reaction. These general insights helped
to validate qualitative notions of force–reactivity relationships that previously had
been supported purely by theoretical arguments.
In addition to pulling on pincer complexes embedded in single, extended polymer
chains, the effect of mechanical action on response was examined in the context of
surface-tethered polymer brushes cross-linked by the pincer complexes 10 [7].
Physical and Materials Applications of Pincer Complexes 345
Fig. 20 Results of AFM experiments to determine most probable force vs. loading rate of
mixtures of 10b and two different teathered polymers capped with pyridine units. Reproduced
from [51] with permission from Copyright # 2006 American Chemical Society
The mechanics of these brushes was examined using an AFM, but this time by
dragging the AFM as a lateral probe of physical properties (friction) or by pulling the
tip from the surface to characterize adhesion. Figure 21 shows a diagram of the cross-
linked brush and the AFM tip dragging across the surface.
Rather remarkably, whether the friction increased or decreased was observed to
depend on the N-alkyl substituent; adding a pincer-PdII cross-linker with the
“faster” methyl substituents caused the friction to go down, while adding a cross-
linker with the “slower” ethyl substituents caused the friction to increase. The
unexpected and divergent response is reminiscent of that observed in the shear
thickening vs. shear thinning behavior of the macroscopic networks, and while
uncovered by the ability afforded by the pincer complexes to probe structure–-
activity relationships of this nature, a complete physical picture for the behavior has
not yet been established. From a materials engineering point of view, however, we
note that the pincer complexes are able to induce dramatic changes in fundamental
surface properties, and that these changes are reversible, as demonstrated by the
addition of a competing DMAP ligand to bring the thin film friction properties back
to their original values [7].
Fig. 21 Representation of
grafted polymer brushes
cross-linked by pincer
complex 10. The tribological
properties of the brush can be
probed by an atomic force
microscope. Reproduced
from [7] with permission
from Copyright # 2006 John
Wiley and Sons
actuator [67] (a unit that translates the applied force to the mechanophore).
Bielawski et al. were able to meet these criteria when developing their mechanor-
esponsive catalyst. The bis-functional SCS-pincer complex is embedded in the
center of a polymer via coordination to two pyridine capped polymer chains, in a
manner reminiscent of Kersey et al.’s AFM studies (Fig. 22). Instead of applying
force via an atomic force microscope, however, the mechanical force is generated
by subjecting a solution to pulsed sonication, which generates transient
elongational flow fields that rapidly stretch the polymer. The applied forces break
the chain at the mechanophore [the pincer–pyridine ligand interaction (Fig. 22)]. As
established by a variety of control experiments and characterizations, these
transformations are mechanically, rather than thermally, induced.
Once pincer–pyridine dissociation was induced mechanically, the free palladium
was shown to be catalytically active in palladium-catalyzed carbon–carbon bond
formation. When the pincer infused polymers (14) were sonicated in the presence of
2-fluorobenzyl cyanide (17), and N-tosylbenzylimine (18a) for 2 h, a 93 % conver-
sion to the coupled product 19 was observed (Fig. 23). Structure–activity
relationships found in the conventional catalyst were also observed in the mechani-
cally activated catalyst: increasing the electron density in the imine led to a
decrease in catalytic efficiency [68]. Another set control experiments confirmed
the necessity of mechanical activation from the precursor under the conditions of
the experiment.
Additional catalytic activity was observed with the freed pyridine moieties (16).
Previously, Willson et al. had shown that pyridine can be used to initiate anionic
polymerization of a-trifluoromethyl-2,2,2-trifluoroethyl acrylate (20) [69]. Draw-
ing inspiration from this earlier work, Beilawski et al. sonicated a solution
containing the pincer bearing polymer, 14 and the substrate 20 for 2 h. Sonication
removed the pincer “protecting group” from the pyridine and induced the expected
polymerization, with product P(20) ultimately being obtained in 42% yield
(Fig. 24). Consistent with the palladium-catalyzed systems, no polymerization
Physical and Materials Applications of Pincer Complexes 347
Fig. 22 When a polymer chain that contains the pincer complex (14) is subjected to sonication,
the pyridine–metal bond is broken, resulting in the pincer complex capped chain (15), and the
pyridine capped chain (16). Reproduced from [65] with permission from Copyright # 2010
American Chemical Society
3 General Conclusions
As testified by the bulk of this volume, pincer complexes have gained popularity
largely through their ability to effect chemical transformations. Nonetheless, the ease
of synthesis and handling, stability in a wide range of chemical environments, and the
availability of handles for structural manipulation has provided a wealth of
opportunities to use pincer complexes in a range of physical applications. They
have been used to build complicated nanostructures and metallodendrimers by both
convergent and divergent techniques. They have provided a mechanism for rapid and
selective post-synthetic modification of random and block copolymers, and as the
glue for new classes of multilayer thin films with impressive stability. They have
served as probes of fundamental polymer physical behavior, and played a key role in
seminal discoveries and demonstrations in the burgeoning field of polymer mecha-
nochemistry. Looking ahead, it seems likely that pincer complexes will provide
additional benefits to research in materials science, and for the same reasons that
they have been so useful to date: they are compact, functional, and dependable, with
metallosupramolecular coordination behavior that functions reliably even in complex
environments. Their past utility in the context of materials is therefore not surprising,
nor is likely to be their future use in a growing range of physical applications.
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Index
A B
Acrolein, a-cyanopropionates, 257 Bathophenanthroline, 94
Agostic pincer complexes, 21, 30 Binaphthol, 257
Aldehydes, asymmetric reductive Bioimaging, 123
aldol reaction, 261 Biosensors, 123
Aldol coupling, reductive, 209 2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1,
Aldol reactions, 203, 205 3,4-oxa-diazole, 94
reductive, 259 Bisallylpalladium, 213
Alkenes, asymmetric Bisamino-pincers, 3
hydrosilylation, 258 Bis(azolylmethyl)phenyl, (NCN)NiBr, 154
Alkyl hydride anionic complex, 43 2,6-Bis(2-benzimidazolyl)pyridine, 114
Alkynes, cross-coupling, 256 Biscycloplatination, 8
Alkynylation, 263, 264 1,8-Bis(diphenylphosphino)anthracene
Allenyl silanes, 223 (DPA), 97, 313
Allyl–allyl coupling, 213, 218 Bismuth, 189
Allylation, 203, 211 fluorides, 189
Allylboronic acids, 218 phosphates, 191
Allyl stannanes, 220 1,3-Bis(N-methyl-benzimidazol-
Allyltributyltin, 257 2-yl)benzene, 112
Amine borane, dehydrogenation, 271 Bis(oxazoline)pyridine (pybox), 245
Ammonia borane, 273 Bis(oxazolinyl)phenyl (phebox), 152, 243
Ammonia, N–H activation, 293 Bisphosphine-pincer ligand, 3
Antimony, 189 1,3-Bis(1-pyrazolyl)benzene, 121
fluorides, 190 1,3-Bis(2-pyridyl)-4,6-dimethylbenzene, 112
phosphates, 191 1,3-Bis(pyrrolidinothiocarbonyl)benzene, 93
Arenes, 253 1,3-Bis(8-quinolyl)benzene, 121
Arsenic, 189 b-Borylation, 263
Aryl–aryl cross-coupling, 227 2-Bromoisophthalic acid, 248
Arylmethyl-based scaffolds,
C(sp3)-metalated, 303
Asymmetric catalysis, 243 C
Atom transfer radical addition Carbometalated pincer complexes, 289
(ATRA), 225 Carbon dioxide reduction, Rh/Ir, 293
353
354 Index
Q T
Quinone methides, 21, 23, 43 Terdentate ligands, 49
Thallium, 178
Thioquinone methide complexes, 21
R Tin, 178, 180
Reactive intermediates, 21, 23 Transfer hydrogenation, 235
Reversible networks, 339 Triarylmethyl-based scaffolds,
Rhodium, 203, 246, 293 C(sp3)-metalated, 305
catalysts, 243 Triazine pincers, 57
quinone methide, 23 Tributyl allyl stannane, 212
Ruthenium, 89, 108, 203, 249 a-Trifluoromethyl-trifluoroethyl
catalysts, 243 acrylate, 346
pincers, redox potentials, 79 Tris(2-pyridyl)benzene, 112
S V
Sb, 188 Vinyl aziridines, 218
SCS ligands, 92, 131 Vinyl cyclopropanes, 218
Sensing, 89
Single electron transfer (SET), 226
Sn, 178, 180 W
Solar cells, dye-sensitised (DSSCs), 89, 110 White-light-emitting devices (WOLEDs), 124
Spin-orbit coupling (SOC), 90
Stannylation, 221
Stannylenes, 181 X
Steric effects, 49 Xylylene complexes, 21