Organometallic Chemistry
Organometallic Chemistry
Organometallic Chemistry
CH2
H2C
Co
Fe(CO)3
CHO
(CO)8Co2
CO/H2
CHO
+
Me
Me
Me
F3C
OTBS
N
BOC
F3C
H2/Pd-C
(w/desilylation)
F3C
OH
OH
N
BOC
99:1
78%
N
BOC
Cy3P
Ir
N
PF6
Crabtree's Catalyst
Crabtree
OH
N
BOC
158:1
91%
Cl
Kumada Coupling
CH3
Ni(PPh3)2Cl2
+ MeMgBr
R'
I
Larock Indole Synthesis
(first step is a Heck reaction)
N
R
O
Ring Closing Metathesis
Me
R'
R"
5% Pd(OAc)2/Ph3P
N
R
Ph
Mo(CHt-Bu)(NAr)[OCMe(CF3)2]2
C2H4
R"
Ph
Me
Me O
Me O
Alkyne Cyclotrimerization
TMS
CpCo(CO)2
TMS
H
TMS
TMS
Asymmetric Catalysis
Commercial Preparation of Menthol
Me
Me
Me
(S)-BINAP-Rh(I)
Me
NEt2
Me
Me
NEt2
Me
Me
PPh2
PPh2
Me
CHO
OH
Me
(S)-BINAP
Me
Me
()-menthol
(R,R)-PNNP-Rh(I)
+ H2
CO2H
NHCOCH3
Ph
Me
N
(R,R)-PNNP =
N
Ph
CO2H
PPh2
NH2
PPh2
HN
Me
aspartame
CO2H
C
M
alkyl
carbene
(alkylidene)
alkynyl
alkenyl
carbyne
(alkylidyne)
Complexes that do chemistry involving intermediates containing transition metal-carbon bonds (Broader
Definition -- Most Widely Accepted). This definition encompasses many of the catalytic processes that we are
interested in.
(Ph3P)3RhCl (Wilkinson's catalyst-olefin hydrogenation and isomerization)
Pd(PPh3)4 (Cross-couping and Heck Chemistry) PdCl2/CuCl2 (Wacker catalyst)
Rh2(OAc)4 (Carbenoid Insertion Chemistry)
Any M-C Bond Containing Species, where M is more electropositive than carbon (Broadest Definition -Applied by Organometallics)
SiR4
PR3
SnR4
AlR3
Transition Metals
Li
Be
Na
Mg
Ca
Sc
Ti
Rb
Sr
Zr
Cs
Ba
La*
Hf
11
12
Al
Si
Co
Ni
Cu
Zn
Ga
Ge
Ru
Rh
Pd
Ag
Cd
In
Sn
Os
Ir
Pt
Au
Hg
Tl
Pb
Cr
Mn
Fe
Nb
Mo
Tc
Ta
Re
LATE
14
10
EARLY
13
The d Orbitals
z
y
x
dx2y2
dz2
dxz
dxy
dyz
bonding
CH
Malkyl
CC
vis
MCl
CCl
MOR
COR
Dative:
M
:CO
:PR3
vis F3B
:OEt2
bonding
vis
CR2
R2C
CR2
Cl
Cl
CO
CO
bonding
Bonding Representations
CO
H2C
H2C
CH2
Co
OC
Fe
Cl
CO
CO
Fe(CO)3
Pd
Ph3P
PPh3
Cl
CO
A Primer on MO Theory
Ionization Potential
M X
orbital overlap
M X
Electronegativity
H
2.2
Li
1.0
16
17
N
3.0
O
3.4
F
4.0
Si
1.9
P
2.2
S
2.6
Cl
3.1
Ga
1.8
Ge
2.0
As
2.2
Se
2.5
Br
2.9
Cd
1.7
In
1.6
Sn
1.8
Sb
2.0
Te
2.1
I
2.6
Hg
2.0
Tl
1.6
Pb
1.9
Bi
2.0
Po
2.0
At
2.2
13
14
Be
1.6
B
2.0
C
2.5
Na
0.9
Mg
1.3
Al
1.6
K
0.8
Ca
1.0
Sc
1.3
Ti
1.5
V
1.6
Cr
1.6
Mn
1.6
Fe
1.8
Co
1.9
Ni
1.9
Cu
1.9
Zn
1.7
Rb
0.8
Sr
1.0
Y
1.2
Zr
1.3
Nb
1.6
Mo
2.1
Tc
1.9
Ru
2.2
Rh
2.3
Pd
2.2
Ag
1.9
Cs
0.8
Ba
0.9
La*
1.1
Hf
1.3
Ta
1.5
W
2.3
Re
1.9
Os
2.2
Ir
2.2
Pt
2.3
Au
2.5
10
11
12
15
Electronegativity
Covalent bonds in late organotransition
metal complexes are relatively non-polar
Some important trends:
Early metals
Main Group
Transition metals
Late metals
M+ XGroup
element
Pauling EN
Sc
cost
$$$$$
More Ionic
Ti
1.3
1.5
$
Zr
$$
Nb
$$
Hf
cost:
$
$$
$$$
$$$$
$$$$$
Very cheap
cheap
moderate
expensive
very expensive
$
Mo
$$
Ta
$$
$
Tc
$$$
W
$$$
$
Ru
$$$$$
Re
$$$$
$
Rh
$$$$
Os
1.9
$
Pd
2.3
$$$$$
Ir
2.2
$$$$$
Ni
1.9
2.2
1.9
10
Co
1.8
1.9
2.3
Fe
1.6
2.1
1.5
Mn
1.6
1.6
1.3
Cr
1.6
1.3
$$$
M-X
More Covalent
2.2
$$$$
Pt
2.2
$$$$$
2.3
$$$$$
M+ X
Ti
Most
electropositive
Cr
Mn
Fe
MX
Co
Ni
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Hf
Ta
Re
Os
Ir
Pt
Stronger
bonds
Most
electronegative
hydridic
Cp2Zr
H
Cl
Schwartz's
Reagent
acidic
(CO)4CoH
Catalyst for
oxo process
Cp2Zr
Cl
D(H-X) in kcal/mol
120
110
100 neopentyl
Ph
(CH3) > 1 > 2 > 3
Me
Vy
Pentyl
Cy
90
40
50
60
70
80
90
D(Ir-X) in kcal/mol
In general, if an equilibration mechanism exists (and it does), alkyl groups will isomerize to 1 product.
suggested
as due to
steric
hinderance
M
M
ML
:L
(or ML+)
MCO
:C O
(or MCO+)
MPR3
:PR3
(or MP+R3)
M
:L
M
M
or
+
+
Backbonding
:PR3
:CO
R2C
CR2
C
M
CO
M
C
d
CO as donor
C
C
CO as acid
alkene as donor
d
*
alkene as acid
Dewar-Chatt-Duncanson model
-Backbonding
Spectroscopic evidence:
More backbonding
M
CO
(cm1)
2143
H3BCO
2164
Ni(CO)4
2060
Weaker CO
Co(CO)4
1890
Fe(CO)42
1730
Mn(CO)43
1670
Chemical evidence:
HCo(CO)4
8.4
HCo(CO)3PPh3
15.4
Cr(CO)44
1500
C
C
M
C
alkene as donor
d
*
alkene as acid
If M is electron donating, backbonding is strong:
Cp2(Me)Zr+
Complex is unstable
Cp2Zr
Cp2Zr
Complex is stable
Olefin rendered nucleophilic
The more electron-rich the metal, the more -backbonding is seen. More
metallacyclopropane character.
1
*Cp
1.337
Ti
1.536
*Cp
nC4H9
ZrCp2
PMe3
nC4H9
nC4H9
ZrCp2
PMe3
180
135.8
nC4H9
120
1.286
1.20
metallacyclopropene-much closer
1.34
Phosphines
M
PR3
PR3 as donor
But very electron deficient phosphines can be excellent ligands for TM's
(e.g. PCl3, P(OR)3, etc.)
2.24
Ph2
P
Cl
Pt
P
Cl
(CF3)2
P
d
2.37
2.17
2.32
R
R
R
d
R
R
R
*
Orpen Chem. Comm. 1985, 1310
Cone Angle
R
R
R
P
2.28
Ph2P
104
P(OMe)3
107
PMe3
118
PPhMe2
122
PPh2
125
PEt3, PPh2Me
132
PPh3
145
PCy3
170
P(t-Bu)3
182
P(o-tol)3
194
PCy2
SPhos
240*
iPr
XPhos
256*
PCy2
MeO
iPr
PF3
OMe
75
Me
90
CO
95
Cp
136
*For a different view-"% Buried Volume: Nolan Chem. Commun. 2010, 46, 841
Electron Counting
Method 1: The Dative Ligand Formalism
Assume all ligands are bound datively:
MCO
M
:CO
MCl
M+
:Cl
MCH3
M+
:CH3
MH
M+
:H
M=O
M+2
::O2
Common Ligands
X-
(-1
c h arge)
2 e-
1
-allyl
-1
-1
-1
B: (Lewis Bases-neutral)
-allyl
:CO
C a r b on monoxide is probably the most important ligand in terms of
industrial applications.
R3P :
cyclopentadienyl (Cp)
-systems
neutral
-2
Me
Me
Me
Me Me
alkynes
neutral
-2
olefins
Me
Me
Me
Me
M
M
neutral
1,3-dienes
neutral
4
O
M
bridging carbon monoxide
neutral
OR
RO
-1, 2 e-
OR
RO
-1, 4 e-
OR
RO
-1, 6 e-
-1 for each
metal
2 for each
metal
M
metal-metal bond
neutral
1 for each
metal
metal carbene
neutral
CH2
CH2
metal alkylidene
-2
CO
Example:
OC
OC
Step 1:
Mn+
Mn
CO
H
Mn0 is d7
so Mn+ is d6
(6 unshared electrons)
Step 3:
:CO
OC:
CO
:CO
:H
OC:
:CO
Step 2: N/A
Step 4:
MnI (d6)
H
5 x CO
6
2
10
18 e
(coordinatively saturated
complex)
CO
Example:
OC
OC
Step 1:
:CO
OC:
Mn
:CO
CO
Mn
CO
OC:
:CO
Step 2: N/A
Step 4:
Mn
H
5 x CO
7
1
10
18 e
(same answer)
:PPh3
Pd0
Ph3P:
Pd0 d10
4 x PPh3
:PPh3
Rh+
:PPh3
10
8
18 e
:Cl
Ph3P:
RhI d8
3 x PPh3
Cl
6
16 e
Rh+
O
O
O2
::
O
O
V++++
acac
RhI d8
2 x COD
8
8
16
:O:
acac
acac:
4 e, 1 charge
VIV d1
2 x acac
8
4
oxo
13 e
The 18 e "rule" often fails for early TM's
"Non-Innocent" Ligands
Hapticity
3-allyl
CH2
M
CH2
4 electron donor
(1) charge
1-allyl
M
M
C
H2
2 electron donor
(1) charge
[(PMe3)2Pd(allyl)]+
Me3P
Me3P
Me3P
Pd+
Me3P
Me3P:
H2
Me3P:
H2
Me3P:
:C
Pd2+
Pd+
:C
Pd2+
Me3P:
PdII d8
2 x PMe3
8
4
PdII d8
2 x PMe3
8
4
1-allyl
3-allyl
14 e
16 e
1.!Oxidative-Addition
X
LnM(a+2)
Y
Br
(Ph3P)2Pd
Br
Pd
PPh3
Ph3P
X
LnM(a+2)
2.!Reductive-Elimination
LnM(a)
X-Y
Y
Note there is a decrease in formal oxidation state (-2) of the metal.
Example:
TMS
Ph3P
Pd
Ph3P
(Ph3P)2Pd
TMS
This is the most important means to form carbon-carbon bonds.
Review: Hartwig Inorg. Chem. 2007, 46, 1936
L nM(a) A + X-Y
t-Bu
Br H
Br 2
Cp2Zr
L nM a
L nM(a) X + A-Y
t-Bu
H
Br
Cp2Zr
Cl
Cl
t-Bu
H
Br
This is an important path for d0 (e.g., Zr(IV) ) metals to get substrates on and off the metal.
4. Ligand Substitution
A) Simple Exchange-can be either associative or dissociative
L nM
tBu3P
L n-1M
CO2Me
Cl
tBu3P
Cl
Example:
Stille ACIEE, 1986, 25, 508
tBu3P
Cl
Pd
MeO 2C
tBu3P
B) Transmetallation
Pd
Pd
L nM
X +
Ph
PPh 3
Pd
M'R
PPh 3
Br
e.g., CH 3Li
L nM
M'-X
or nBu 3Sn
Ph
+
Note there is
no change in
formal
oxidation state
of the metal.
nBu 3Sn
PPh 3
nBu 3SnBr
Pd
PPh 3
forward:
insertion of
olefins and
alkynes into M-H
and M-R'
C
LnM
LnM
LnM
LnM
This is the primary means by which small molecules (e.g., CO, alkenes, alkynes) are
incorporated into metal complexes and subsequently into organic products.
AcN(H)
Br
CO/H2O
L
L= Ph3P
Pd
L
CO
Br
reverse: For R=
H, -hydride
elimination
reactions
CHNF, Ch 6
L
cf. Tsuji, Palladium Reagents and
Catalysts
Pd
L
O
AcN(H)
CO
Ph3P Rh
Ph3P
H
CH3
Ph3P Rh CO
Ph3P
CH3
B) Oxidative-Cyclization Processes
ox state of M
a
insertion
ox state of M L M
n
a+2
LnM
ox state of
M a+2
LnM
This process is termed oxidative cyclization since two organic groups are coupled together and the metal is formally oxidized.
Cp2Zr
TMS
TMS
TMS
insertion
NBn
Cp2Zr
NBn
Cp2Zr
NBn
CH2
R
LnM
LnM
OR'
LnM
CH2
H2C
OR'
OR'
LnM
LnM
Bn
Bn
N
MLn
H2C
R
R'
Petasis, JACS 1990, 112, 6392
Grubbs, Pine Comp. Org. Syn., Vol 5, Ch 9.3, p 1115
R'
Bn
Example:
R
R'
MLn
CH3
CH3
H3C
LnM+
Nuc-
Nuc
Nuc
LnM
+
MLn
MLn
Nuc
X
LnM +
Nuc-
LnM+
X-
Nuc-
LnM +
Cl
CpRu
PF 6
CpRu
OMe
OH
HO
TBSO
TBSO
EtO
O
O
N
H
H
N
88%
N(H)Boc
EtO
N
H
OMe
OH
O
H
N
N(H)Boc
O
Pearson TL 2005, 46, 3966
L nM
L nM
H
tBu
Me3Si
Me3Si
Mo
Me3Si
SiMe3
Me3Si
tBu
M
P
CH 3
OAr
M= Hf, Zr
SiMe3
L nM
H
R'
CH 3
Mo
b) -abstraction Reaction
h
N
L nM
iPr 2P
CH2
M
P
OAr
R'H
PiPr 2
N
R
LnM
R'
R Reductive
Elimination
-hydride
elimination
LnM
LnM
R'
R
R'H
-abstraction
LnM
R'H
This process is a concerted process which accomplishes the same overall transformation. This can be important
in cases in which -hydride elimination would lead to an unstable intermediate.
Cp2Zr
Cp2Zr
CH4
H
Me
d0
Cp2Zr
Me
Cp2Zr
Cp2Zr
CH4
LnM(a+2)
X-Y
!The reaction proceeds with a net increase in formal oxidation state of the metal center.
Favored in electronic rich (e.g., low valent) complexes.
Electron donating ligands (e.g., trialkylphosphines) increase the facility of oxidative addition.
Disfavored in electron deficient (e.g., high valent or cationic) complexes.
Electron withdrawing ligands (e.g., CO) decrease the facility of oxidative addition reactions.
!The reactions are, in principle, reversible via reductive-elimination pathways.
!Often ligand dissociation is required:
LnM
18 e- complex
(Often unreactive)
L4M 18 e- complex
(e.g, M= Pd)
-L
-nL
Ln-1M
L2M or L1M
16 e- complex
14 or 12 e- complex
!Oxidative-Addition is a generic descriptor providing no mechanistic information. Many mechanistic pathways fall
under this term, including SN2, radical, 3-centered, ionic and bimetallic processes.
Crabtree, Ch 6, CHNF, Ch 5, Stille Review
R
LnM
LnM
LnM
X
OC
Ph3P
Ir
PPh3
CH3
Ph3P
Cl
Cl
Stereochemical
Evidence:
Ir
CO
PPh3
Ph3P
Cl
(Ph3P)4Pd
Ph
(S)
Cl
CO
PPh3
CH3
CH3
H D
Ir
trans product
Cl
inversion
PPh3
PPh3
Pd
Ph
(R)
D H
Ph
RX: simple alkyls primary > secondary (mostly radical) >>> tertiary (radical)
Until recently, not very synthetically useful--often see radical and reduction products.
Pearson JACS 1982, 102,
1541
X Ar
OR X
OH
LnM
X-Y
LnM
LnM
Y
LnM
R
LnM
LnM
R
H
CO
Ph3P
"Vaska's Complex"
PPh3
Ph3P
MLn
Ir
Cl
PPh3
OC
Ir
Cl
M
H
H
d
L
OC
CO
H
OC
0.84
free H2 0.74
LnM
LnM-X
R
LnM
X
-L
L3Pt
L4Pt
16e-
Br
e- transfer
L
Br
L3Pt
Br
Pt
Br
Pt
L
Stille, Review,CHNF, Ch 5, Crabtree, Ch 6
Br
Ph3P
CO
+ CH3CH2-Br
Ir
Cl
Ph3P
Cl
PPh3
Ir
CO
PPh3
CH2CH3
via: CH3CH2 + IrCl(CO)L2
RIrII Cl(CO)L2 + RX
RIrII Cl(CO)L2
R(X)IrIIICl(CO)L2 + R
[(Cy3P)2Pd]
Me
(Cy3P)2Pd
Br(Cl)
Me
8
Br(Cl)
Ph
Ph
Br
(tBu2(Me)P)2Pd
0 C/Et2O
tBu
Me
tBu
Pd
Me
tBu
Br tBu
Entry
1
2
R Br
Br
Me
Me
Br
L Pd
G [kcal/mol]
1.0
19.5
0.19
20.3
Br
Me
Me
Br
0.054
21.0
<0.0001
>24.0
Me
Entry
G [kcal/mol]
P(t-Bu)2Me
19.5 (0 oC)
PCy3
20.0 (0 oC)
P(t-Bu)2Et
P(t-Bu)3
L Pd
Br
THF, 0 oC
L = P(t-Bu)2Me
krel
Me
Me
Me
Me
P
P
Pd
Pd
Me
Me
Favored
conformer
much more
hindered at Pd
Pd
+ R
M X
LnM
M X
R
For ArX: Pd: Pd(PPh3)4 X= I > Br > OTf >> Cl (requires electron withdrawing subs--however, more modern
systems allow for this to occur under reasonable conditions), however OTf > Br for PdCl2(PPh3)2 (Catalyst
better able to coordinate to oxygen of triflate).
Possible Mechanisms:
LnM +
electron
transfer
ArX
nucleophilic
aromatic
substitution
LnM
ArX
LnMX Ar
MLn
X
concerted
For LnNi + ArX: the top pathway is usually followed (electron transfer)
For LnPd + ArI: the bottom pathway is followed
LnM(Ar)X
MLn
X
Oxidative-Addition--Key Features-5
Examining the reaction of (PPh3)4Pd + ArI:
(PPh3)4Pd
(PPh3)3Pd + PPh3
Keq >> 1
(PPh3)3Pd
(PPh3)2Pd + PPh3
Keq << 1
(PPh3)2Pd + ArI
(PPh3)2Pd(Ar)I
For reactions of
H is the same in toluene or THF. This indicates that there is no solvent coordination involved in the
oxidative addition step. It is most consistent with a mechanism in which there is "no charge development in
the transition state," i.e. the concerted pathway.
Kochi has previously shown that there are large variations (a factor of ~9) in the rates of oxidative addition of
LnNi(0) to ArX with a change in solvent polarity. This is a reaction which is believed to proceed via the electron
transfer pathway.
Amatore calculates that electron transfer from L2Pd to ArX is "more endergonic than from LnNi(0) to the
same halide" by 35 kJ/mol (8.4 kcal/mol).
Amatore Organometallics, 1990, 9, 2276
Oxidative-Addition--Vinylic Substrates
Alkenyl Halides and Triflates: Pd: I, OTf, Br commonly employed. Recent work indicates that Cl is viable: Ni:
Cl and Br most studied, I also works.
Mechanistic Issues:
1)!Reactions proceed with retention of double bond geometry; inconsistent with free radical mechanisms.
2)!Ni(0) > Pd (0) > Pt (0), but Pd by far the most synthetically useful. Use of nickel catalysts can often lead to
radical products.
3)!Reactions of vinyl bromides are faster than reactions with CH3I.
Postulated Mechanism:
X
Precomplexation
R''
X
LnM
X
R''
LnM
R''
LnM
R
R'
R'
R'
Transformations of vinyl chlorides involving oxidative addition: Fu JACS, 2000, 122, 4020
Stille, Review; CHNF, Ch 5; Stille ACIEE 1986, 25, 508
Stepwise Transformation
Br
Br
Br
Ar
PdL2
PdL2
PdL2
<30 C
Ar
Ar
L2= DPPF =
CH3MgX
Fe
PPh2
PPh2
Me
PdL2
Me
PdL2
Ar
Me
Ar
"L2Pd"
Ar
stable below 20 C
observable at < 0 C
Brown Inorg. Chem. Acta. 1994, 220, 249
Reductive-Elimination Summary
X
LnM(a)
LnM(a+2)
X-Y
Y
!!Cis orientation of X and Y is required.
!!Relatively favorable for electron deficient complexes. Relatively disfavored for electron !rich complexes;
reductive-elimination leads to a complex in which the metal has a !reduced formal oxidation state.
!!Rate enhanced by bulky ligands; reductive-elimination leads to a complex with decreased coordination number.
!!Reductive elimination from a coordinatively saturated intermediate is favored as is formation of an
electronically stable product (i.e., reaction to form an unstable molecule is disfavored).
!!Reductive elimination has been shown to proceed with retention of !configuration at carbon.
Ph3P
Pd
CH3
Ph3P
PPh3
Ph
(R) D
HD
O
OTBS
PPh3
Ph
CH3
Ph
H3C
H D
L2Pd
Pd
(Ph3P)2Pd
H
CHNF, Ch 5,Stille, Review
H D
HD
OTBS
L2Pd
L2= DPPF
O
Review: Hartwig Inorg. Chem. 2007, 46, 1936
Pd
Pd
P
R'
P2Pd
R R'
R'
P
larger
bite angle = 89
Ph
Pd
P
Ph2
(DPPP)Pd
Me
1/2=30 min @ 35 C
Me
bite angle = 97
Ph2
P
Ph
(DPPF)Pd
Pd
Fe
P
Ph2
Me
1/2~15 min @ 0 C
Me
t-Bu
DPPBz
Ar R
40-100 C
krel
Me
>600
CH2Ph
>250
CH2C(O)Ph
31
CH2CF3
1.7
CH2CN
CF3
no rxn
Ar =
Me
Pt
Ar3P
Ph
Ar3P
Ph
CH4
Pt
Ar3P
Ph
Ar
kobs
(x104)
C6H4Cl
9.2
C6H5
4.5
C6H4Me
1.4
C6H4OMe
0.47
reaction rate unaffected by addition of Ar3P. Therefore, reaction doesn't proceed by either an associative
or a dissociative pathway.
reaction shown to be intramolecular by crossover experiments.
Ar3P
Ar3P
Pt
CH3
H
Ar3P
Ar3P
Pt
CD3
D
Ph
Ph
Ph
Ar3P
CH4
Pt
Ar3P
+ CD4
Ph
very little CH3D or CD3H was seen
Halpern JACS 1978, 100, 2915
R
>
M
H
R
>
M
R
R
M
R
b2
hybrid orbital
1b2
1a1
a1
b2
M
H
1b2
1a1
a1
Ph
85 C
Pd
Fe
1.5 h, 90%
N(tolyl)2
P
Ph2
Ph2
P
Ph
25 C
Pd
Fe
1.5 h, 80%
N(H)Ph
P
Ph2
Ph2
P
Ph
0 C
Pd
Fe
P
Ph2
N
H
Me
1.5 h, 64%
PhPN(tolyl)2
HNPh2
PhN(H)(i-Bu)
Me
Ar Nuc
L2Pd
Nuc
C P
Relative Rates:
>
>
C S
>
C N
C O
Ar
Ar
L1Pd
L2Pd
>
Nuc
Ar Nuc
Nuc
L1Pd
Ar Nuc
L2Pd
Implies that reductive elimination from Pd(II) complexes faster with monodentate than with chelating ligands.
X
reductive elimination
LPd
Ar NR2
L2Pd
NR2
-hydride elimination
Ar H
Hartwig JACS 1996, 118, 3626
Hartwig Inorg. Chem. 2007, 46, 1936
X + A-B
L nM(a)
L nM(a)
A +
B-X
Me
Me
N
Cp2Zr
PhSiH 3
Me
Me
N
Cp2Zr
H 2(Ph)Si
H
H
Me
Me
Cp2ZrSi(Ph)H2
Me
Jordan OM 2005, 24, 2688
Cp*
Cp*
Ru
Ru
Ph 3P
Ph 3P
Ph 3P
Ph 3P
Me
Cp*
Me
Ru
Bcat
Ph 3P
Ph 3P
+ MeBcat
H
O
+
H-B
O
HBcat
Hartwig, JACS, 1994, 116, 1839
Review: Waterman OM 2013, 32, 7249
C
LnM
LnM
!Although the reaction is usually referred to as a carbon monoxide insertion reaction, mechanistic studies have
shown that it actually takes place by an alkyl migration pathway.
!Requires cis orientation of R, CO.
!Relative migratory aptitude:
LnM
CH3 >
LnM
sp3 carbon
>>
LnM
CF3
LnM
very rare
sp2 carbon
t-Bu
H D
Fe(CO)2
Cp
Ph3P
THF
t-Bu
CO
Fe
H D
O
Cp PPh3
Whitesides JACS 1974, 96, 2814
LnM
R
R
>>
R
>
R
>
>
R
>
>>
R
CHNF, Ch 6
-hydride
R elimination
LnM
LnM
R'
R'
!Requires open coordination site. Relatively slow for coordinatively saturated complexes. One manifestation of
this can be seen in changing from simple phosphines to chelating bis-phosphines. This inhibits phosphine
dissociation and keeps the complex coordinatively saturated.
!Principle mode of decomposition for metal alkyls.
!Important step in olefin isomerization.
!Shows geometric effects; slower in metallacyclic compounds.
L2Pt
L2Pt
L2Pt
nBu
nBu
L2Pt +
H3C
krel
1
L2Pt +
H3C
L2Pt
CH3
H3C
L2Pt + H3C
Optimum transition
state has Pt, H and
the 2 C's coplanar
best when
H-C-C-Pt
angle is 0
L2Pt
1
4
10-4
Cf. Crabtree
CHNF, Ch 6
Catalytic Cycles-1-Hydrogenation
Ln+1M
Ligand-loss
(exchange)
LnM
+ H2
Oxidative-Addition
18 e-
LnM
16 e-
+2
Ligand-loss
(exchange)
-L
H
+2
Ln-1M
16
+2
Insertion
e-
Ln-1M
CH3
H
H
Ligand-add
(exchange)
+2
16 e-
Ln-1M
18 e-
Ligand-add
(exchange)
+L
H
+2
LnM
18
- C2H6
e-
CH3
LnM
Reductive
Elimination
16 e-
Catalytic Cycles-2-Hydroformylation
HRh(CO)2L2 18 e-CO Ligand loss
(exchange)
CHO
R
HRh(CO)L2
16 eR
red-elim
Ligand add
(exchange)
H
H
R
O
ox-add
Rh
CO
L
H
L 18 e-
Rh
Regiochemistry
Determining
insertion
H3C
Rh(CO)L2
CO
18 e-
+H2
migratory
insertion
Rh(CO)L2
CHO
16 eR
O
migratory
insertion
Rh(CO)L2 16 e+CO
Me
Iso
+H2 ox-add
Rh(CO)2L2
18 e-
H
R
Rh(CO)L2 red-elim
18 e-
CH3
olefin
hydrogenation
HN(R1)R2
N(R1)R2
Ar
L/ Pd
L2Pd
Ar
N(R1)R2
BHCl
14
RE
RE
+ Ar-Cl
OA
B:
O
L2Pd
Ar
Cl
Ar
Cycle B
16
L2Pd
Cl
N(R1)R2
Cycle A
L2Pd
16
16
MI
BHCl
+ CO
LE
O
O
B:
Ar
L2Pd
X
Review: Barnard OM 2008, 27, 5402
HN(R1)R2
16
Ar
Nucleophilic Attack or
Reductive Elimination
N(R1)R2
n+1 p
n+1 s
nd
9n
non-bonding
Ln
n ML
bonding
Examples
ZrCp2
ZrCp2
Cp
Cp
Zr4+
Zr2+
Cp
Cp
ZrII d2
2 x Cp
2-benzyne
12
2
16 e
ZrIV d0
0
2 x Cp
12
benzene dianion
4
16 e
Backbonding does not change e count, but it does change formal oxidation state.
An example of why oxidation state is really only a formalism
in organometallic chemistry (although often a useful one)
Five coordinate:
Six coordinate:
cis
L
trans
L
L
Leq
Leq
Lax
L
Leq
L
L
Lax
Four coordinate:
trans
L
L
L
L
L
tetrahedral
L
cis
M
L
square
planar
L
L
square
pyramidal
trigonal
bipyramidal
octahedral
PdCl2(PR3)2
(Wilkinson's catalyst)
Ph3P
Cl
Cl
Ir
OC
Pd
PPh3
Pd
Cl
X
M
Octahedral ML6:
dz2
dx2-y2
eg
is larger for:
1. 2nd and 3rd row TM's
2. "strong ligands"--e.g.,
CO (-effects), Ph3P, H(more electron density,
accentuates LF effects)
6 et2g
12 e-
See Crabtree, Ch 1, 2
Ligand-centered
dxz
dyz
dxy
y
x
L
L
L
M
L
L
L
d6 octahedral
dx2-y2, dz2
d8
Complex
L
L
M
L
z
y
x
dx2-y2, dz2
if -Backbonding
eg
if -Donation
eg
eg
eg
t2g
t2g
t2g
t2g
More tendency to be 18 e-
electron density is
removed from the metal,
lowering the energy of
these orbitals (by mixing
with the empty ligand *)
See Crabtree, pp17-19
interaction with
filled ligand
orbitals, raises
the energy of
these orbital
(electron-electron
repulsion)
MO Diagram for
Square Planar d8 Complex
L
z
y
x
dxy
(between x-y axis)
2 2
d x -y
ligand centered