Journal of Organometallic Chemistry: Sciencedirect

Journal of Organometallic Chemistry 751 (2014) 399e411
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Journal of Organometallic Chemistry

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A comparative study of the reactivity of the lightly stabilized cluster

[Os3(CO)8{m3-Ph2PCH2P(Ph)C6H4}(m-H)] towards tri(2-thienyl)-,
tri(2-furyl)- and triphenyl-phosphine
Arun K. Raha a, Md. Nazim Uddin a, Shishir Ghosh a, b, Abdur R. Miah a,
Michael G. Richmond c, Derek A. Tocher b, Ebbe Nordlander d, Graeme Hogarth b, *,
Shariff E. Kabir a, *
a
Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh
b
Department of Chemistry, University College London, 20 Gordon Street, London WC1H OAJ, UK
c
Department of Chemistry, University of North Texas, 1155 Union Circle, Box 305070, Denton, TX 76203, USA
d
Inorganic Chemistry Research Group, Chemical Physics, Center for Chemistry and Chemical Engineering, Lund University, P.O. Box 124, SE-22100 Lund,
Sweden
a r t i c l e i n f o a b s t r a c t
Article history: Reactions of the lightly stabilized triosmium cluster [Os3(CO)8{m3-Ph2PCH2P(Ph)C6H4}(m-H)] with tri(2-
Received 28 May 2013 thienyl)phosphine (PTh3) and tri(2-furyl)phosphine (PFu3) are described and compared to analogous
Received in revised form reactions with PPh3. At room temperature, a number of products are isolated: [Os3(CO)10(m-dppm)] from
9 August 2013
CO addition, [Os3(CO)8(PR3){m3-Ph2PCH2P(Ph)C6H4}(m-H)] from phosphine addition, [Os3(CO)9(PR3)(m-
Accepted 12 August 2013
dppm)] from phosphine and CO addition and [Os3(CO)8(PR3)2(m-dppm)] from addition of two equivalents
of phosphine. The latter are shown by NMR and X-ray diffraction to exist as 1,2-isomers, whereby one
Keywords:
phosphine is bound to the non-dppm-substituted center and the second shares an osmium atom with
Triosmium
Phosphines
one end of the diphosphine. Heating 1,2-[Os3(CO)8(PTh3)2(m-dppm)] at 100 C results in its clean
Addition reactions isomerization to the 1,1-isomer in which both monodentate phosphines are located on the same osmium
Isomerization atom. Prolonged heating of [Os3(CO)8(PR3)2(m-dppm)] (R ¼ Th, Ph) at 110 C gives [Os3(CO)9(PR3)(m-
Carbon-phosphorus bond cleavage dppm)] and the new lightly stabilized clusters [Os3(CO)7(PR3){m3-Ph2PCH2P(Ph)C6H4}(m-H)], the latter
DFT studies being formed by loss of phosphine and CO with concurrent metalation of a phenyl ring. Heating
[Os3(CO)8(PFu3)2(m-dppm)] at 110 C gives [Os3(CO)9(PFu3)(m-dppm)] together with the carbon-
phosphorus bond cleavage products [Os3(CO)7(m-PFu2)(m3-h2-C4H2O)(m-H)(m-dppm)] and [Os3(CO)7(m-
PFu2)(m3-h2-C6H3CH3)(m-H)(m-dppm)]. All new compounds were characterized by analytical and spec-
troscopic techniques together with single crystal X-ray diffraction analysis of nine clusters. Density
functional theory (DFT) calculations have been carried out on isomers of [Os3(CO)8(PR3)2(m-dppm)] in
order to understand the observed isomer ratios.
Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction cluster [Os3(CO)8{m3-Ph2PCH2P(Ph)C6H4}(m-H)] (1) [11], first prepared

by Smith and coworkers upon decarbonylation of [Os3(CO)10(m-
The high reactivity associated with electronic and coordinative dppm)], is not formally unsaturated but it behaves in this way as the
unsaturation in mononuclear transition metal complexes has been relatively weak interaction of the orthometalated phenyl group with
widely exploited in developing novel chemical behavior and in the triosmium center is easily removed. Consequently, 1 has been
catalysis. In comparison, despite the widespread interest in cluster shown to have a rich chemistry [12,13], which is dominated by ligand
chemistry [1] the number of unsaturated low-valent clusters is addition rather than carbonyl substitution. For example, it undergoes
extremely limited [2e14]. Amongst the most studied examples of facile and reversible carbonylation at 25 C to afford saturated
electronically unsaturated clusters is [Os3(CO)10(m-H)2] [10], whose [Os3(CO)9{m3-Ph2PCH2P(Ph)C6H4}(m-H)] (3) which in turn adds
unsaturation derives from its 46e count. The diphosphine-substituted further CO to regenerate the parent cluster 2 (Scheme 1) [11]. Recently,
Hall, Richmond and coworkers have investigated these processes in
* Corresponding authors. some detail [14]. Their results show that carbonylation of 1 proceeds
E-mail address: [email protected] (S.E. Kabir). via an intermediate [Os3(CO)8{m-Ph2PCH2P(Ph)C6H4}(m-H)] (A), in
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.08.027
400 A.K. Raha et al. / Journal of Organometallic Chemistry 751 (2014) 399e411
(CO)3 Ph2 Ph
(OC)4 Os Os P P
CO H Ph2
P
Os P (OC)3 Os Os (CO)3
(CO)3 Ph2
2 Os B
25 oC, 2d (CO)3
110 oC - 2CO CO
Ph Ph
P P
Ph2 25 oC Ph2
P CO, 2h P
(OC)3 Os Os (CO)3 (OC)3 Os Os (CO)3
110 oC
H Os 4h H Os
(CO)2 (CO)3
1 3
Ph CO
P
Ph2
P
(OC)3 Os Os (CO)3
H Os
(CO)2 A
Scheme 1.
which an osmium-carbon bond involving the orthometalated phenyl dppm)] (2), [Os3(CO)8(PR3){m3-Ph2PCH2P(Ph)C6H4}(m-H)] (4e6),
moiety of the dppm ligand is broken, and a subsequent (rate-deter- [Os3(CO)9(PR3)(m-dppm)] (7e9) and [Os3(CO)8(PR3)2(m-dppm)] (10e
mining) associative step involving the addition of CO to 12) (Scheme 2). Smith and coworkers previously reported that re-
the unsaturated intermediate, yielding [Os3(CO)9{m-Ph2PCH2P(Ph) action of 1 with ca. one equivalent of PPh3 gives 2, 6 and 11, while 9
C6H4}(m-H)] (3). Further carbonylation of 3 then proceeds via a has been prepared by Johnson, Lewis and coworkers from the reac-
reductive coupling with formation of [Os3(CO)9(m-dppm)] (B) as an tion between [Os3(CO)9(NCMe)(m-dppm)] and PPh3 [13d,18] Cluster
intermediate, a process which proceeds via an agostic intermediate, 2 results from addition of two molecules of CO to 1, with the CO
followed by two discrete p-aryl complexes (Scheme 1) [14]. presumably originating from cluster degradation. The characteriza-
Phosphines are widely used as ligands in transition metal- tion and mode of formation of each of the other product types is
catalyzed reactions since they offer a wide variety of stereo- discussed separately in the following sections.
electronic properties that can substantially influence the course of a
catalyzed reaction. One of the most widely utilized is triphenyl- 2.2. Phosphine addition products [Os3(CO)8(PR3){m3-Ph2PCH2P(Ph)
phosphine which has been reported to react smoothly with 1 to afford C6H4}(m-H)] (4e6)
[Os3(CO)8(PPh3){m3-Ph2PCH2P(Ph)C6H4}(m-H)] and [Os3(CO)8(PPh3)2
(m-dppm)] [13d]. Over the past decade the chemistry of tri(2-furyl) Clusters 4e6 are adducts of 1 and PR3. The PPh3 complex 6 has
phosphine (PFu3) [15,16] and tri(2-thienyl)phosphine (PTh3) [17] has previously been spectroscopically characterized [13d] and data for
been developed. Sterically they are akin to PPh3; however, the 4 and 5 are similar. The 31P{1H} NMR spectrum of each displays a
electron-withdrawing nature of the 2-heteroaryl rings makes them pair of doublets, assigned to the dppm ligand, and a singlet for the
poorer s-donors than PPh3 [17m]. This has been exploited in certain PR3 ligand. The absence of coupling between the two phosphines
catalytic reactions, with PFu3-containing catalysts often being more suggests that either they are bound to different metal atoms or two
active than traditional PPh3-based catalysts [16]. One aspect of our phosphorus atoms bound to the same osmium lie cis to one
recent work has been a comparison of these three ligands in similar another. Each cluster has a high field resonance in its 1H NMR
chemical systems [15cef,17geh] and herein we focus on an investi- spectrum indicative of a bridging hydride (d 18.1 for 4; e18.4 for
gation of the comparative reactivity of the three phosphines towards 5; e15.9 for 6). In order to fully elucidate the structures we have
lightly stabilized 1. carried out an X-ray diffraction study of 5, the results of which are
summarized in Fig. 1. The structure of 5 is very similar to
2. Results and discussion [Os3(CO)8(PPri3){m3-Ph2PCH2P(Ph)C6H4}(m-H)] [13d] and contains a
triangle of osmium atoms with three distinct osmiumeosmium
2.1. Reaction of [Os3(CO)8{m3-Ph2PCH2P(Ph)C6H4}(m-H)] (1) with bond distances [Os(1)dOs(2) 2.8961(6), Os(1)dOs(3) 2.8569(7)
PR3 (R ¼ Th, Fu, Ph) and Os(2)dOs(3) 3.0883(6) A] the longest being spanned by the
hydride (located and refined in the structural analysis). The PFu3
Treatment of 1 with two equivalents of the requisite phosphine at ligand occupies an equatorial coordination site on Os(2), while the
25 C in dichloromethane gave four product types; [Os3(CO)10(m- diphosphine is axially coordinated to Os(2) and Os(1) which
A.K. Raha et al. / Journal of Organometallic Chemistry 751 (2014) 399e411 401
Ph
P
Ph2 PR3 (CO)3 Ph2
P
(OC)3 Os Os (CO)3 (OC)4 Os Os P
RT
H Os Os P
(CO)2 (CO)3 Ph2
2
1 PTh3 (6%)
PFu3 (6%)
PPh3 (11%)
Ph +
P CO
Ph2 OC (CO)3 Ph2
P
Os (CO)3 + Os Os P
(OC)3 Os
R3 P
CO Os P
H Os(CO)2 (CO)3 Ph2
PR3
4, R = Th (13%) 7, R = Th (11%)
5, R = Fu (12%) 8, R = Fu (8%)
6, R = Ph (29%) 9, R = Ph (19%)
CO CO
R 3P (CO)3 Ph2 Fu3P (CO)3 Ph2
Os Os P + Os Os P
OC CO
Fu3P
CO CO Os P
Os P (CO)3 Ph2
R3 P Ph2
CO
12, (66%)
10, R = Th (54%)
11, R = Ph (24%)
Scheme 2.
facilitates coordination of the C6H4 moiety to Os(3). The P(2)-Os(2)- that for 9 and also other complexes of the type [Os3(CO)9L(m-
P(3) bond angle of 94.96(6)o accounts for the lack of coupling dppm)] [L ¼ P(OMe)3, PHPh2] [18,19]. Each 31P{1H} NMR spectrum
between these phosphorus atoms. In [Os3(CO)8(PPri3){m3-Ph2 consists of a pair of doublets attributed to the diphosphine and a
PCH2P(Ph)C6H4}(m-H)], the osmiumephosphorus bonds sharing singlet for the monodentate phosphine, while all 1H NMR spectra
the same osmium atom [2.442(7) and 2.411(8) A] are significantly contain a triplet in the aliphatic region assigned to the methylene
longer than the third [2.334(8) A] which Smith attributed to the protons of the dppm ligand. We have determined the crystal
extra electron-density on this osmium atom due to the presence of structures of both 7 and 9, which are shown in Figs. 2 and 3,
the PPri3 ligand [13d]. In 5, the osmiumephosphorus bond respectively. Both are as expected; all phosphorus atoms lie in the
involving P(2) of the diphosphine ligand and Os(2) is significantly equatorial plane and the gross structural features are similar to
longer [2.427(2) A] than the others [2.352(2) and 2.332(2)
A]. These those of [Os3(CO)9(PHPh2)(m-dppm)] [19] and [Os3(CO)10(m-dppm)]
differences may be a result of the better p-acceptor ability of PFu3, [20]. It seems likely that 7e9 result from the intermediate forma-
while in contrast PPri3 is a good s-donor ligand. By analogy to the tion of 4e6, followed by carbonyl addition, a process in which the
carbonylation of 1 that has been studied experimentally and monodentate phosphine also migrates to another osmium center.
computationally [14] (vide supra), it is likely that the phosphine In a separate experiment we have shown that 6 reacts with CO to
adducts 4e6 are formed in a similar fashion to 3; that is via the afford 9 as one of the products. This transformation is probably in
isomeric mono-metalated intermediate [Os3(CO)8{m-Ph2PCH2P(Ph) competition with phosphine addition to 4e6 (see below), with the
C6H4}(m-H)] (A) (Scheme 1). actual product distribution governed by the relative amounts of
free CO and phosphine present in solution.
2.3. Phosphine and carbonyl addition products [Os3(CO)9(PR3)(m-
dppm)] (7e9) 2.4. Double phosphine addition products [Os3(CO)8(PR3)2(m-dppm)]
(10e12)
Clusters 7e9 formally result from addition of both CO and
phosphine to 1, followed by carbon-hydrogen bond formation. The The fourth cluster type, and the major product in the case of all
PPh3 complex, 9, has previously been reported by Johnson, Lewis three phosphines, is [Os3(CO)8(PR3)2(m-dppm)] (10e12) which
and coworkers [18]. Spectroscopic data for 7e8 are in accord with formally result from addition of two equivalents of phosphine to 1
Fig. 3. ORTEP diagram of the molecular structure of [Os3(CO)9(PPh3)(m-dppm)] (9),

Fig. 1. ORTEP diagram of the molecular structure of [Os3(CO)8(PFu3){m3-Ph2
showing 50% probability thermal ellipsoids. Ring hydrogen atoms are omitted for
PCH2P(Ph)C6H4}(m-H)] (5), showing 50% probability thermal ellipsoids. Ring hydrogen
clarity. Selected bond distances (
A) and angles( ): Os(1)dOs(2) 2.8768(4), Os(1)d
atoms are omitted for clarity. Selected bond distances (
A) and angles( ): Os(1)dOs(2)
Os(3) 2.9149(5), Os(2)dOs(3) 2.8871(4), Os(1)dP(1) 2.3349(11), Os(2)dP(2)
2.8961(6), Os(1)dOs(3) 2.8569(7), Os(2)dOs(3) 3.0883(6), Os(1)dP(1) 2.352(2),
2.3311(11), Os(3)dP(3) 2.3560(11), Os(2)dOs(1)dOs(3) 59.796(6), Os(1)dOs(2)d
Os(2)dP(2) 2.4267(19), Os(2)dP(3) 2.3316(18), Os(3)dOs(1)dOs(2) 64.931(10),
Os(3) 60.757(10), Os(2)dOs(3)dOs(1) 59.447(10), P(3)dOs(3)dOs(1) 102.82(3),
Os(1)dOs(2)dOs(3) 56.921(15), Os(1)dOs(3)dOs(3) 58.148(15), P(3)dOs(2)dOs(3)
P(3)dOs(3)dOs(2) 160.89(3), C(7)dOs(3)dP(3) 99.94(15), C(8)dOs(3)dP(3)
111.81(5), C(4)dOs(2)dP(3) 101.1(2), P(3)dOs(2)dP(2) 94.96(6), P(1)dOs(1)dOs(3)
90.84(15), P(1)dC(10)dP(2) 112.1(2).
85.32(5), P(1)dOs(1)dOs(2) 86.81(5), C(6)dOs(3)dC(12) 89.2(3), C(12)dOs(3)d
Os(1) 91.6(2), P(1)dC(10)dP(2) 107.5(4).
have determined the crystal structures of 10 and 12, the results of
with concomitant carbonehydrogen bond formation. Two isomeric which are shown in Figs. 4 and 5, respectively. For 10 there are
forms are seen (Chart 1), and these are denoted as the 1,1- and 1,2- two independent triosmium clusters (and three molecules of
isomer. Smith and coworkers previously found that PPh3 afforded dichloromethane) in the asymmetric unit.
only the 1,2-isomer, whereas other phosphines and phosphites In the solid state, 10 exists as the 1,2-isomer while 12 is a 1,1-
gave the 1,1-isomer [13d]. With P(OMe)3 both isomers were formed isomer. Akin to the situation for 11, [Os3(CO)8{P(OMe)3}2(m-
and could be separated by TLC, and the X-ray structure of the 1,1- dppm)] [13d] and [Os3(CO)8(PHPh2)2(m-dppm)] [19], all phos-
isomer was reported. The same authors also reported the X-ray phorus atoms in both 10 and 12 occupy equatorial coordination
structure of 1,2-[Os3(CO)8(PPh3)2(m-dppm)] (11) [13d] and we have sites. Spectroscopic data for non-crystalline samples of 10 showed
previously shown that [Os3(CO)8(PHPh2)2(m-dppm)] is a 1,1-isomer the presence of both isomers in solution (Scheme 3). Thus, the 31P
[19]. In order to confirm the nature of the different isomers, we {1H} NMR spectrum displays two sets of resonances in an approx-
imate 5:1 ratio. The 1,2-isomer (10a) is the major form character-
ized by signals at 20.7 (dd, JPP ¼ 50.2, 9.2 Hz), e27.3 (d,
JPP ¼ 50.2 Hz), e39.3 (d, JPP ¼ 9.2 Hz) and 51.8 (s) ppm due to the
four non-equivalent phosphorus atoms, while the minor 1,1-isomer
(10b) appears as two singlets at 29.1 and 40.8 ppm. In contrast,
spectroscopic data for 12 show that only the solid-state structure
(1,1-isomer) exists in solution, being observed as two equal in-
tensity singlets. We have carried out VT NMR studies of both 10 and
11 in d8-toluene. No significant changes were seen in the 31P NMR
spectrum of 1,2-[Os3(CO)8(PPh3)2(m-dppm)] (11) upon warming to
80 C. Above this temperature, the bright yellow solution lightened
and a number of new resonances appeared due to irreversible
changes resulting from loss of PPh3 (see following section). Heating
a sample of pure 1,2-[Os3(CO)8(PTh3)2(m-dppm)] (10a) to 80 C led
to no significant change; however, between 80 and 100 C, the
disappearance of 10a was observed with concomitant formation of
the 1,1-isomer 10b. Scheme 3 illustrates this transformation.
Maintaining this sample at 100 C for several hours led to the
appearance of a number of new resonances associated with phos-
phine loss and secondary rearrangement products (see following
section).
Fig. 2. ORTEP diagram of the molecular structure of [Os3(CO)9(PTh3)(m-dppm)] (7), In order to further probe the relative stability of 1,1- and 1,2-
showing 50% probability thermal ellipsoids. Ring hydrogen atoms are omitted for isomers of 10e12, we have performed density functional theory
A) and angles( ): Os(1)dOs(2) 2.9141(4), Os(1)dOs(3) (DFT) calculations on both sets of isomers. Fig. 6 shows the opti-
2.8829(3), Os(2)dOs(3) 2.8856(4), Os(1)dP(3) 2.3345(12), Os(2)dP(2) 2.3370(11), mized structures for 10a and 10b, where the 1,2-isomer is 4.8 kcal/
Os(3)dP(1) 2.3242(11), Os(3)dOs(1)dOs(2) 59.703(8), Os(3)dOs(2)dOs(1)
59.610(6), Os(1)dOs(3)dOs(3) 60.687(9), P(3)dOs(1)dOs(2) 100.42(3), P(3)dOs(1)d
mol lower in energy than the 1,1-isomer. The ligand disposition in
Os(3) 159.03(3), C(2)dOs(1)dP(3) 104.26(15), C(1)dOs(1)dP(3) 91.30(14), P(1)d the optimized structure of 10a agrees nicely with the solid-state
C(10)dP(2) 111.6(2). structure that is exhibited in Fig. 4. On the basis of the
thermodynamically less stable isomer 10b forms is far from clear.

We have kinetically and computationally investigated the isomer-
ization behavior of related phosphines at Os3(CO)10(PP) clusters
(where PP ¼ diphosphine) [21]. In these examples, the isomeriza-
tion was well-behaved and does not involve the dissociation of
the diphosphine ligand from the cluster. In the case of the
Os3(CO)8(PR3)2(dppm) clusters investigated in this study, no
attempt has been made to study this isomerization process by DFT
because of the complexity of the reaction which is likely to proceed
via the loss of a monodentate PR3 ligand, followed by ligand capture
at the putative unsaturated cluster Os3(CO)8(PR3)(dppm).
The geometry of cluster 12 was subjected to DFT analysis and the
optimized structure (not shown) was consistent with the solid-
structure structure. The corresponding 1,2-isomer based on 12
was also optimized and the disposition of the ancillary ligands
about the cluster polyhedron paralleled the DFT structure
computed for 10a. The energy difference for the two PFu3-based
clusters is small (DG ¼ 0.8 kcal/mol) and favors that of the crys-
tallographically observed isomer. While the ground-state energy
difference between the two isomers is small, the activation barrier
is assuredly much greater and no equilibration of the two isomers is
Fig. 4. ORTEP diagram of the molecular structure of one of the unique molecules of
[Os3(CO)8(PTh3)2(m-dppm)] (10), showing 50% probability thermal ellipsoids. Ring
expected at room temperature.
hydrogen atoms are omitted for clarity. Selected bond distances (
A) and angles( ):
Os(1)dOs(2) 2.8882(4), Os(1)dOs(3) 2.9128(5), Os(2)dOs(3) 2.9112(4), Os(1)dP(1) 2.5. Thermolysis of [Os3(CO)8(PR3)2(m-dppm)] (10e11): phosphine
2.3269(17), Os(2)dP(2) 2.3170(16), Os(3)dP(3) 2.3196(17), Os(2)dP(4) 2.3091(16), loss and carbonehydrogen bond activation
Os(2)dOs(1)dOs(3) 60.242(8), Os(1)dOs(2)dOs(3) 60.298(11), Os(2)dOs(3)dOs(1)
59.461(11), P(3)dOs(3)dOs(1) 97.51(4), P(3)dOs(3)dOs(2) 156.97(4), C(7)dOs(3)d
P(3) 92.1(2), P(4)dOs(2)dP(2) 108.09(6), C(4)dOs(2)dP(4) 92.1(2), P(4)dOs(2)d From the variable temperature (VT) NMR studies discussed
Os(1) 159.42(4), P(4)dOs(2)dOs(3) 99.53(4), P(1)dC(65)dP(2) 116.7(3). above, we were aware that the bis(phosphine) complexes 10e11
were unstable at higher temperatures. In order to probe this
behavior, we heated 10e11 independently in toluene which fur-
free-energy difference between 10a and 10b, a Keq value of 3 104
nished two products in each case (Scheme 4). The major product
is computed, and this is in concert with the experimental data and
found in both reactions was [Os3(CO)9(PR3)(m-dppm)] (7 and 9),
the observation of only 10a in the initial synthesis. While heating
resulting from phosphine substitution by CO, while the second
10a furnishes 10b through the formal migration of a single PTh3
products were the new lightly stabilized clusters [Os3(CO)7(PR3)
ligand about the cluster polyhedron, the mechanism by which the
{m3-Ph2PCH2P(Ph)C6H4}(m-H)] (13e14), which are formed upon loss
of both phosphine and CO with concomitant oxidative addition of a
carbon-hydrogen bond.
The molecular structures of 13 and 14 are shown in Figs. 7 and 8,
respectively, with the captions containing selected bond lengths
and angles. The overall structures are very similar to that of 1 apart
from the replacement of an equatorial carbonyl group of 1 by a
phosphine ligand. As in 1, the osmiumeosmium edge that is
simultaneously bridged by the metalated phenyl group and the
hydride ligand [2.747(1) A in 1; 2.7732(7)
A in 13 and 2.7729(7)
A in
14] is significantly shorter than the other two [2.844(1) and
2.834(1) A in 1; 2.8415(7) and 2.8455(8) A in 13; 2.8492(6) and
2.8470(6) A in 14], a condition that reflects the constraining influ-
ence to the two bridging ligands. The most notable feature of 13 and
14 is the position of the phosphine ligand that is bound to the
osmium atom that is not coordinated by the diphosphine. Spec-
troscopic data are consistent with the solid-state structures. Each
31 1
P{ H} NMR spectrum consists of two doublets and a singlet in
1:1:1 ratio, as expected for the three non-equivalent phosphorus
atoms in the cluster, and the hydride resonance in the 1H NMR
spectra appears as a doublet of doublet of doublets. Clusters 13 and
14 are CO substitution products of 1 that are not formed from the
direct reaction of 1 with these phosphines (Scheme 1). This un-
derscores the difference in reactivity between electronically satu-
Fig. 5. ORTEP diagram of the molecular structure of [Os3(CO)8(PFu3)2(m-dppm)] (12), rated and unsaturated carbonyl clusters; the former being
showing 50% probability thermal ellipsoids. Ring hydrogen atoms are omitted for dominated by CO substitution.
A) and angles( ): Os(1)dOs(2) 2.8732(5), Os(1)d The mode of formation of these products (Scheme 4) is not fully
Os(3) 2.8960(5), Os(2)dOs(3) 2.8942(6), Os(1)dP(1) 2.304(2), Os(2)dP(2) 2.308(2), understood, however, given the very similar outcomes of the two
Os(3)dP(3) 2.282(2), Os(3)dP(4) 2.281(2), Os(2)dOs(1)dOs(3) 60.220(14), Os(1)d
Os(2)dOs(3) 60.281(11), Os(2)dOs(3)dOs(1) 59.499(13), P(3)dOs(3)dOs(1)
reactions we assume that they take place by the same mechanism.
154.15(6), P(3)dOs(3)dOs(2) 97.96(6), C(7)dOs(3)dP(3) 99.94(15), C(8)dOs(3)dP(3) For 10, we know from VT NMR studies (see preceding section)
90.1(3), C(7)dOs(3)dP(4) 86.7(2), P(1)dC(11)dP(2) 116.9(5). that heating at 100 C promotes the formation of the 1,1-isomer
Fig. 6. Geometry-optimized structures for the isomeric clusters 10a and 10b. The quoted free-energy (kcal/mol) difference is relative to 10a at room temperature.
10b (Scheme 3). While we cannot show this for 11, we assume that H)(m-dppm)] (15) (40%) and [Os3(CO)7(m-PFu2)(m3-h2-C6H3CH3)(m-
isomerization also occurs but under the conditions required to H)(m-dppm)] (16) (31%) (Scheme 5). Cluster 8 results from phosphine
facilitate this, secondary processes leading to formation of 9 and 14 substitution by CO, while cluster 15 results from a loss of one PFu3
are competitive. Loss of a phosphine from the 1,1-isomers would ligand, coupled with the activation of one carbon-phosphorus bond
result in the unsaturated intermediates, [Os3(CO)8(PR3)(m-dppm)], in remaining the PFu3 ligand. This PeC bond cleavage generates the
which can add CO to give 7 and 9 or undergo CeH activation, fol- observed phosphido and capping furyne (m3-h2-C4H2O) groups in the
lowed by CO loss, to give 13 and 14. Hall and Richmond [14] have product. The isolation of cluster 16 provides evidence for the acti-
recently shown that addition of CO to the intermediate 46-electron vation of the toluene solvent during the thermolysis reaction. An
cluster [Os3(CO)9(m-dppm)] (B) (Scheme 1) is rapid, and it seems independent control experiment has confirmed that the furyne
reasonable to suggest that the same is true for the putative species cluster 15 does not serve as a precursor to 16.
[Os3(CO)8(PR3)(m-dppm)]. The added CO must result from another ORTEP diagrams of the molecular structures of 15 and 16 are
cluster molecule, which, in turn, has undergone CeH activation. depicted in Figs. 9 and 10, and selected bond distances and angles
are listed in the captions. Both are similar to the triruthenium
2.6. Thermolysis of [Os3(CO)8(PFu3)2(m-dppm)] (12): carbone thiophyne and furyne clusters [Ru3(CO)7{m-P(C4H3E)2}(m3-h2-
phosphorus bond cleavage C4H2E)(m-H)(m-dppm)] (E ¼ S, O) [17b]. A m3-h2-C4H2O (in 15) and
m3-h2-C6H3CH3 (in 16) ligand caps the open triangular array of
Heating 12 in toluene for 2 h followed a different course to that of osmium atoms. The hydride was not located directly but it is
10e11, leading instead to the formation of three products; [Os3 believed to span the dppm-bridged edge due to the significant
(CO)9(PFu3)(m-dppm)] (8) (19%), [Os3(CO)7(m-PFu2)(m3-h2-C4H2O)(m- lengthening of this bond [Os(2)dOs(3) 2.9668(4) A in 15; Os(1)d
Os(2) 2.9494(7) A in 16] as compared to the other [Os(1)dOs(2)
2.8508(4) A in 15; Os(2)dOs(3) 2.8527(6) A in 16]. In both, the
phosphido group bridges the open edge of the cluster in a slightly
unsymmetrical fashion [Os(1)dP(1) 2.396(2) and Os(3)dP(1)
2.373(2)
A in 15; Os(3)dP(3) 2.393(2) and Os(1)dP(3) 2.364(2) A in
Fig. 7. ORTEP diagram of the molecular structure of [Os3(CO)7(PTh3){m3-Ph2PCH2P(Ph) Fig. 8. ORTEP diagram of the molecular structure of [Os3(CO)7(PPh3){m3-Ph2PCH2P(Ph)
C6H4}(m-H)] (13), showing 50% probability thermal ellipsoids. Ring hydrogen atoms are C6H4}(m-H)] (14), showing 50% probability thermal ellipsoids. Ring hydrogen atoms are
omitted for clarity. Selected bond distances (
A) and angles( ): Os(1)dOs(2) 2.8415(7), omitted for clarity. Selected bond distances (
A) and angles( ): Os(1)dOs(2) 2.8492(6),
Os(1)dOs(3) 2.7732(7), Os(2)dOs(3) 2.8455(8), Os(1)dP(1) 2.360(2), Os(2)dP(2) Os(1)dOs(3) 2.8470(6), Os(2)dOs(3) 2.7729(7), Os(1)dP(1) 2.331(2), Os(2)dP(2)
2.336(2), Os(3)dP(3) 2.325(2), Os(1)dC(12) 2.362(8), Os(3)dC(12) 2.238(8), Os(3)d 2.324(2), Os(3)dP(3) 2.372(2), Os(2)dC(9) 2.245(9), Os(3)dC(9) 2.430(9), Os(3)d
Os(1)dOs(2) 60.886(16), Os(1)dOs(2)dOs(3) 58.372(11), Os(1)dOs(3)dOs(2) Os(1)dOs(2) 58.260(16), Os(3)dOs(2)dOs(1) 60.830(14), Os(2)dOs(3)dOs(1)
60.742(19), P(1)dOs(1)dOs(3) 110.02(5), P(1)dOs(1)dOs(2) 166.33(5), P(2)dOs(2)d 60.910(15), P(3)dOs(3)dOs(1) 172.19(6), P(3)dOs(3)dOs(2) 111.99(6), P(1)dOs(1)d
Os(3) 77.98(5), P(2)dOs(2)dOs(1) 85.67(5), P(3)dOs(3)dOs(1) 131.33(5), P(3)d Os(3) 84.54(6), P(1)dOs(1)dOs(2) 77.36(6), P(2)dOs(2)dOs(3) 131.01(6), P(2)d
Os(3)dOs(2) 89.25(5), Os(3)dC(12)dOs(1) 74.1(2), C(2)dOs(1)dOs(3) 116.6(3), Os(2)dOs(1) 90.03(6), Os(2)dC(9)dOs(3) 72.6(2), C(5)dOs(2)dOs(3) 117.7(3), C(7)d
C(6)dOs(3)dOs(1) 121.3(3), P(2)dC(10)dP(3) 107.3(4). Os(3)dOs(2) 114.9(3), P(1)dC(8)dP(2) 107.9(4).
CO CO
R3P (CO)3 Ph2 R3P (CO)3 Ph2
Os Os P Os Os P
OC CO
R3P
CO Os P CO
(CO)3 Ph2 Os P
R3P Ph2
CO
1,1-isomer 1,2-isomer
Chart 1.
15) and 1411 (for 16) associated with the molecular ions. NMR
spectra of 15 show that in solution it exists in two isomeric forms.
Thus, the 31P{1H} NMR spectrum consists of two sets of resonances
in 4:1 ratio, each set consisting of two doublets and a doublet of
doublet due to the three phosphorus atoms. Consistent with this,
the aliphatic region of the 1H NMR spectrum exhibits four reso-
nances for the methylene protons of the dppm ligand at d 3.34, 3.10,
Fig. 9. ORTEP diagram of the molecular structure of [Os3(CO)7(m-PFu2)(m3-h2- 2.73, and 2.53 with a relative intensity of 4:1:1:4, respectively,
C4H2O)(m-H)(m-dppm)] (15), showing 50% probability thermal ellipsoids. Ring while the hydride region displays two multiplets at d 17.31
hydrogen atoms are omitted for clarity. Selected bond distances (
A) and angles( ):
and 17.27 also in a 4:1 ratio. We have observed similar isomeri-
Os(1)dOs(2) 2.8508(4), Os(2)dOs(3) 2.9668(4), Os(1)dP(1) 2.3956(17), Os(2)dP(2)
2.3534(17), Os(3)dP(3) 2.3750(16), Os(3)dP(1) 2.3734(16), Os(1)dC(8) 2.119(7), zation of furyne clusters previously [15i] and it most likely arises
Os(3)dC(9) 2.125(6), Os(2)dC(8) 2.427(6), Os(2)dC(9) 2.282(6), Os(1)dOs(2)dOs(3) from the different relative orientations of the oxygen atom in the
84.723(10), P(1)dOs(3)dP(3) 169.29(6), P(1)dOs(3)dOs(2) 76.45(4), P(1)dOs(1)d furyne ring (Chart 2). For 16, the spectroscopic data are in agree-
Os(2) 78.47(4), Os(3)dP(1)dOs(1) 110.60(6), Os(3)dC(9)dOs(2) 84.5(2), Os(1)d ment with the solid-state structure. The 1H NMR spectrum reveals
C(8)dOs(2) 77.3(2), C(9)dOs(2)dC(8) 34.2(2), C(6)dOs(3)dOs(2) 140.03(19), C(4)d
Os(2)dOs(3) 114.7(2), P(2)dC(20)dP(3) 113.6(3).
twenty-nine aromatic hydrogens as series of multiplets from
d 6.32e7.62, with the lone methyl group appearing as a singlet at
d 1.57. The diastereotopic methylene hydrogens and the bridging
16]. Each capping ligand is bound to the cluster through a h2,p- hydride appear as separate resonances centered at d 3.26, 2.50,
interaction, being slightly tilted toward the p-coordination side as and 17.22, respectively. The 31P NMR and ESI mass spectral data
observed in the related thiophyne clusters [Os3(CO)9(m3-k1:h2- are summarized in the experimental section.
PTh2(C4H2S)(m-H)] [17g], [Os3(CO)9(m3-k1:h2-PPh2(C4H2S)(m-H)]
[17d] and [Os3(CO)8(PPh2Th){m3-k1:h2-PTh2(C4H2S)}(m-H)] [17d]. 3. Summary and conclusions
Spectroscopic data support the observed solid-state structures,
for example ESI mass spectra show [MþeH] peaks at m/z 1383 (for In this work we set out to investigate the comparative reactivity
of PTh3, PFu3 and PPh3 towards the lightly stabilized triosmium
cluster [Os3(CO)8{m3-Ph2PCH2P(Ph)C6H4}(m-H)] (1). As detailed in
Scheme 2, even at room temperature the reaction is complex and
leads to a number of different product types. The three phosphines
broadly behave in a similar manner, although it is notable that
PTh3 and PFu3 favor formation of the bis(phosphine) adducts
[Os3(CO)8(PR3)2(m-dppm)] 10 (54%) and 12 (66%) respectively,
while with PPh3 products 6 and 9 (29 and 19%) containing a single
phosphine ligand are more abundant. The key intermediates in
determining this product ratio are likely the saturated mono-
phosphine complexes [Os3(CO)8(PR3){m3-Ph2PCH2P(Ph)C6H4}(m-
H)] (4e6). For both PFu3 and PTh3 the major products are the
bis(phosphine) complexes [Os3(CO)8(PR3)2(m-dppm)] (10 and 12),
further phosphine addition being favored with respect to PPh3 by
both their smaller cone angles (PFu3 133 vs PPh3 148 ) and the
stronger p-acceptor nature, which reduces electron-density at the
cluster center. Both 1,1- and 1,2-isomers were found, and in order to
probe their relative stabilities a series of DFT calculations were
carried out, and the computed free energies (at room temperature)
of the different isomers are in agreement with the experimentally
observed diffraction structures. The bis(phosphine) complexes
were not stable at higher temperatures and converted into a
Fig. 10. ORTEP diagram of the molecular structure of one of the unique molecules of
number of new species, all of which resulted from phosphine loss.
[Os3(CO)7(m-PFu2)(m3-h2-C6H3CH3)(m-H)(m-dppm)] (16), showing 50% probability
thermal ellipsoids. Ring hydrogen atoms are omitted for clarity. Selected bond dis- Interestingly, while PPh3 and PTh3 complexes 10e11 behaved in a
tances (A) and angles( ): Os(1)dOs(2) 2.9494(7), Os(2)dOs(3) 2.8527(6), Os(1)dP(1) similar manner, thermal rearrangement cleavage of the PFu3
2.391(2), Os(2)dP(2) 2.366(2), Os(3)dP(3) 2.393(2), Os(1)dP(3) 2.364(2), Os(1)dC(9) adduct 12 was dominated by carbonephosphorus bond cleavage of
2.169(10), Os(2)dC(10) 2.329(9), Os(2)dC(9) 2.243(9), Os(3)dC(10) 2.093(9), Os(3)d the PFu3 ligand (71% total yield). This resulted in formation of a new
Os(2)dOs(1) 83.803(14), P(3)dOs(1)dP(1) 167.87(8), P(3)dOs(1)dOs(2) 80.03(6),
P(3)dOs(3)dOs(2) 81.61(5), Os(1)dP(3)dOs(3) 109.15(9), Os(1)dC(9)dOs(2) 83.9(3),
furyne cluster 15 together with a related toluene-derived complex
Os(3)dC(10)dOs(2) 80.2(3), C(9)dOs(2)dC(10) 37.0(3), C(1)dOs(1)dOs(2) 130.6(3), 16, formally resulting from exchange of the furyne by the reaction
C(4)dOs(2)dOs(1) 110.2(3), P(1)dC(8)dP(2) 114.8(4). solvent.
CO
Th3P (CO)3 Ph2 CO
Os Os P 100 oC Th3P (CO)3 Ph2
OC CO Os Os P
CO Th3P
Os P CO Os P
Th3P Ph2 (CO)3 Ph2
CO
10a 10b
Scheme 3.
This work demonstrates that the relatively simple procedure of NMR (CDCl3, 25 C): d ¼ 8.54 (m, 2H), 8.24 (m, 2H), 7.67 (m, 15H),
adding two equivalents of a phosphine to 1 is considerably more 7.09 (m, 2H), 6.96 (m, 2H), 6.79 (m, 1H), 6.43 (m, 2H), 6.14 (m, 1H),
complicated than expected, and further that there are some sig- 5.90 (m, 1H), 5.24 (m, 1H), 3.82 (m, 1H), 18.09 (m, 1H). 31P{1H}
nificant differences not only between PPh3 and PFu3/PTh3 but also NMR (CDCl3, 25 C): d ¼ 40.2 (d, JPP ¼ 8.4 Hz, 1P), 33.6 (s,
between PFu3 and PTh3. This mirrors many aspects of our previous 1P), 22.9 (dd, JPP ¼ 63.6, 8.4 Hz, 1P), 28.8 (d, JPP ¼ 63.6 Hz, 1P).
work with these phosphines [15cef,17geh] and suggests that the Characterizing data for 7: Anal. Calcd for C46H31O9Os3P3S3: C, 37.14;
chemistries of these ligands are significantly different warranting H, 2.10. Found: C, 37.39; H, 2.16. IR (CH2Cl2): nCO ¼ 2064 w, 2000 s,
further study. 1980 vs, 1959 sh, 1936 m cm1. 1H NMR (CDCl3, 25 C): d ¼ 7.55 (m,
3H), 7.46 (m, 3H), 7.33 (m, 20H), 7.16 (m, 3H), 4.96 (t, J ¼ 10.6 Hz,
4. Experimental 1H). 31P{1H} NMR (CDCl3, 25 C): d ¼ 24.6 (d, JPP ¼ 53.6 Hz,
1P), 27.6 (d, JPP ¼ 53.6 Hz, 1P), 43.4 (s, 1P). Characterizing data
4.1. General for 10: Anal. Calcd for C57H40O8Os3P4S6: C, 39.35; H, 2.32. Found: C,
39.61; H, 2.39. IR (CH2Cl2): nCO ¼ 2048 w, 1994 s, 1970 vs, 1931
[Os3(CO)12] was purchased from Strem Chemicals Inc. and used m cm1. 1H NMR (CDCl3, 25 C): aliphatic region: 10a: d ¼ 4.68 (t,
without further purification and [Os3(CO)8{m3-Ph2PCH2P(Ph) J ¼ 10.4 Hz); 10b: d ¼ 4.88 (t, J ¼ 10.8 Hz), aromatic region: 10aeb:
C6H4}(m-H)] (1) was prepared according to the published procedure d ¼ 7.49e6.88 (m). 31P{1H} NMR (CDCl3, 25 C): 10a: d ¼ 20.7 (dd,
[11]. Triphenylphosphine, tri(2-thienyl)phosphine and tri(2-furyl) JPP ¼ 50.2, 9.2 Hz), 27.3 (d, JPP ¼ 50.2 Hz), 39.3 (d,
phosphine were purchased from E. Merck, Acros Organics and JPP ¼ 9.2 Hz), 51.8 (s); 10b: d ¼ 29.1 (s), 40.8 (s).
Aldrich, respectively, and used as received. All reactions were car-
ried out under a nitrogen atmosphere using standard Schlenk 4.3. Reaction of [Os3(CO)8{m3-Ph2PCH2P(Ph)C6H4}(m-H)] (1) with
techniques. Reagent-grade solvents were dried by standard PFu3
methods prior to use. Infrared spectra were recorded on a Shi-
madzu FTIR 8101 spectrophotometer. NMR spectra were recorded To a CH2Cl2 solution (20 mL) of 1 (50 mg, 0.042 mmol) was
on Bruker DPX 400 instruments. Elemental analyses were per- added PFu3 (20 mg, 0.086 mmol) and the mixture was then stirred
formed by Microanalytical Laboratories, University College London. at 25 C for 5 h. The solvent was removed under reduced pressure
and the residue chromatographed by TLC on silica gel. Elution with
4.2. Reaction of [Os3(CO)8{m3-Ph2PCH2P(Ph)C6H4}(m-H)] (1) with hexane/CH2Cl2 (3:2, v/v) gave four bands which afforded the
PTh3 following compounds in order of elution: [Os3(CO)10(m-dppm)] (2)
(3 mg, 6%) as yellow crystals, [Os3(CO)8(PFu3){m3-Ph2PCH2P(Ph)
To a CH2Cl2 solution (20 mL) of 1 (50 mg, 0.042 mmol) was C6H4}(m-H)] (5) (7 mg, 12%) as yellow crystals, [Os3(CO)9(PFu3)(m-
added PTh3 (24 mg, 0.086 mmol) and the mixture was then stirred dppm)] (8) (5 mg, 8%) as yellow crystals from hexane/CH2Cl2 at 4 C
at 25 C for 8 h. The solvent was removed by rotary evaporation and and [Os3(CO)8(PFu3)2(m-dppm)] (12) (46 mg, 66%) as orange crys-
the residue chromatographed by TLC on silica gel. Elution with tals from hexane/C2H4Cl2 at 4 C. Characterizing data for 5: Anal.
hexane/CH2Cl2 (7:3, v/v) gave four bands which afforded the Calcd for C45H31O11Os3P3: C, 38.29; H, 2.22. Found: C, 38.52; H, 2.26.
following compounds in order of elution: [Os3(CO)10(m-dppm)] (2) IR (CH2Cl2): nCO ¼ 2027 m, 2003 vs, 1991 s, 1956 m, 1935 m,br cm1.
(3 mg, 6%) as yellow crystals, [Os3(CO)8(PTh3){m3-Ph2PCH2P(Ph) 1
H NMR (CDCl3, 25 C): d ¼ 8.14 (m, 1H), 7.19 (m, 18H), 6.89 (m, 1H),
C6H4}(m-H)] (4) (8 mg, 13%) as yellow crystals, [Os3(CO)9(PTh3)(m- 6.69 (m, 2H), 6.65 (m, 2H), 6.40 (m, 1H), 6.35 (m, 1H), 6.06 (m, 1H),
dppm)] (7) (7 mg, 11%) as yellow crystals and [Os3(CO)8(PTh3)2(m- 5.90 (m, 1H), 5.33 (m, 1H), 3.61 (m, 1H), 18.36 (m, 1H). 31P{1H}
dppm)] (10) (40 mg, 54%) as orange crystals after recrystallization NMR (CDCl3, 25 C): d ¼ 53.3 (s, 1P), 22.7 (d, JPP ¼ 67.2 Hz,
from hexane/CH2Cl2 at 4 C. Characterizing data for 4: Anal. Calcd 1P), 14.0 (d, JPP ¼ 67.2 Hz, 1P). Characterizing data for 8: Anal.
for C45H31O8Os3P3S3: C, 37.03; H, 2.14. Found: C, 37.29; H, 2.19. IR Calcd for C46H31O12Os3P3: C, 38.38; H, 2.17. Found: C, 38.63; H, 2.23.
(CH2Cl2): nCO ¼ 2025 m, 2001 vs, 1987 s, 1949 m, 1932 m, br cm1. 1H IR (CH2Cl2): nCO ¼ 2065 w, 2029 w, 2001 s, 1983 vs, 1967 sh, 1937
Ph
P
Ph2
R3P P
10, R = Th 110 oC 7, R = Th (58%) Os Os (CO)3
+
11, R = Ph 9, R = Ph (52%) (OC)2
H Os 13, R = Th (28%)
(CO)2 14, R = Ph (36%)
Scheme 4.
O
CH3
Fu2P Fu2P
110 oC (CO)2 Ph
2 (CO)2 Ph2
12 8 + (OC)3 Os Os P
+ (OC)3 Os Os P
19% Os P
(CO)2 Os P
H Ph2 (CO)2 H Ph2
15 40% 16 31%
Scheme 5.
m cm1. 1H NMR (CDCl3, 25 C): d ¼ 7.97 (m, 2H), 7.69 (m, 2H), 7.65 as green crystals after recrystallization from hexane/CH2Cl2 at 4 C.
(m, 2H), 7.51 (m, 2H), 7.34 (m, 15H), 6.88 (m, 2H), 6.69 (m, 2H), 6.45 The third band gave a minor unidentified product. Characterizing
(m, 2H), 4.33 (m, 1H), 4.20 (m, 1H). 31P{1H} NMR (CDCl3, 25 C): data for 13: Anal. Calcd for C44H31O7Os3P3S3: C, 36.91; H, 2.19.
d ¼ 56.8 (s, 1P), 27.4 (d, JPP ¼ 53.4 Hz, 1P), 24.8 (d, JPP ¼ 53.4 Hz, Found: C, 37.18; H, 2.24. IR (CH2Cl2): nCO ¼ 2031 vs, 1990 vs, 1977 s,
1P). Characterizing data for 12: Anal. Calcd for C57H40O14Os3P4: C, 1956 m, 1918 s cm1. 1H NMR (CDCl3, 25 C): d ¼ 8.12 (m, 1H), 7.89
41.65; H, 2.46. Found: C, 41.86; H, 2.53. IR (CH2Cl2): nCO ¼ 1993 s, (m, 2H), 7.60 (m, 15H), 7.11 (m, 3H), 6.98 (m, 3H), 6.56 (m, 1H), 6.23
1967 vs, 1927 m cm1. 1H NMR (CDCl3, 25 C): d ¼ 7.43 (m, 6H), 7.31 (m, 2H), 6.15 (m, 1H), 4.78 (m, 1H), 3.77 (m, 1H), 12.16 (ddd,
(m, 20H), 6.47 (m, 6H), 6.28 (m, 6H), 4.87 (t, J ¼ 10.4 Hz, 2H). 31P{1H} J ¼ 10.4, 9.2, 1.8 Hz, 1H). 31P{1H} NMR (CDCl3, 25 C): d ¼ 15.1 (d,
NMR (CDCl3, 25 C): d ¼ 28.3 (s, 2P), 50.6 (s, 2P). JPP ¼ 71.8 Hz, 1P), 19.8 (d, JPP ¼ 71.8 Hz, 1P), 25.7 (s, 1P).
4.6. Thermolysis of [Os3(CO)8(PPh3)2(m-dppm)] (11)

4.4. Reaction of [Os3(CO)8{m3-Ph2PCH2P(Ph)C6H4}(m-H)] (1) with
PPh3
A toluene solution (15 mL) of 11 (40 mg, 0.023 mmol) was
heated to reflux for 30 min. The solvent was removed by rotary
PPh3 (20 mg, 0.086 mmol) was added to a CH2Cl2 solution (20 mL)
evaporation and the residue chromatographed by TLC on silica gel.
of 1 (50 mg, 0.042 mmol) and the mixture was then stirred at 25 C
Elution with hexane/CH2Cl2 (7:3, v/v) developed three bands. The
for 7 h. The solvent was removed under reduced pressure and the
first and second bands gave [Os3(CO)9(PPh3)(m-dppm)] (9) (18 mg,
residue subjected to TLC on silica gel for chromatographic separation.
52%) as yellow crystals and [Os3(CO)7(PPh3){m3-Ph2PCH2P(Ph)
Elution with hexane/CH2Cl2 (7:3, v/v) gave four bands which afforded
C6H4}(m-H)] (14) (12 mg, 36%) as green crystals after recrystalliza-
the following compounds in order of elution: [Os3(CO)10(m-dppm)]
tion from hexane/CH2Cl2 at 4 C. The third band gave a minor un-
(2) (6 mg, 11%) as yellow crystals, [Os3(CO)9(PPh3)(m-dppm)] (9)
identified product. Characterizing data for 14: Anal. Calcd for
(12 mg, 19%) as yellow crystals, [Os3(CO)8(PPh3)2(m-dppm)] (11)
C50H37O7Os3P3: C, 42.48; H, 2.64. Found: C, 42.83; H, 2.72. IR
(17 mg, 24%) as orange crystals and [Os3(CO)8(PPh3){m3-Ph2
(CH2Cl2): nCO ¼ 2103 m, 2061 m, 2044 vs, 2012 s, 1964 w, 1940 w
PCH2P(Ph)C6H4}(m-H)] (6) (18 mg, 29%) as yellow crystals after
cm1. 1H NMR (CDCl3, 25 C): d ¼ 7.95 (m, 2H), 7.81 (m, 2H), 7.62 (m,
recrystallization from hexane/CH2Cl2 at 4 C. Characterizing data for
6H), 7.43 (m, 3H), 7.35 (m, 10H), 7.13 (m, 7H), 6.98 (m, 1H), 6.90 (m,
9: Anal. Calcd for C52H37O9Os3P3: C, 42.50; H, 2.54. Found: C, 42.82; H,
2H), 6.64 (m, 1H), 4.75 (m, 1H), 3.68 (m, 1H), 12.15 (ddd, J ¼ 18.4,
2.61. IR (CH2Cl2): nCO ¼ 2060 m, 2028 w, 1997 s, 1976 vs, 1964 sh, 1933
10.8, 7.6 Hz, 1H). 31P{1H} NMR (CDCl3, 25 C): d ¼ 14.2 (s, 1P), e14.7
m cm1. 1H NMR (CDCl3, 25 C): d ¼ 7.50 (m, 6H), 7.35 (m, 29H), 4.93
(d, JPP ¼ 74.5 Hz, 1P), e20.5 (d, JPP ¼ 74.5 Hz, 1P).
(t, J ¼ 10.4 Hz, 2H). 31P{1H} NMR (CDCl3, 25 C): d ¼ 0.8 (s, 1P), 24.6
(d, JPP ¼ 52.2 Hz, 1P), 27.7 (d, JPP ¼ 52.2 Hz, 1P).
4.7. Thermolysis of [Os3(CO)8(PFu3)2(m-dppm)] (12)
4.5. Thermolysis of [Os3(CO)8(PTh3)2(m-dppm)] (10) A toluene solution (15 mL) of 12 (30 mg, 0.018 mmol) was
heated at 110 C for 2 h. The solvent was removed by rotary
A toluene solution (15 mL) of 10 (30 mg, 0.017 mmol) was heated evaporation and the residue separated by TLC on silica gel. Elution
to reflux for 3 h. The solvent was removed under reduced pressure with hexane/CH2Cl2 (1:1, v/v) developed six bands. The second,
and the residue separated by TLC on silica gel. Elution with hexane/ third and fifth bands gave [Os3(CO)7(m-PFu2)(m3-h2-C4H2O)(m-H)(m-
CH2Cl2 (7:3, v/v) developed three bands. The first and second bands dppm)] (15) (10 mg, 40%) as colorless crystals, [Os3(CO)9(PFu3)(m-
gave [Os3(CO)9(PTh3)(m-dppm)] (7) (15 mg, 58%) as yellow crystals dppm)] (8) (5 mg, 19%) as yellow crystals and [Os3(CO)7(m-PFu2)(m3-
and [Os3(CO)7(PTh3){m3-Ph2PCH2P(Ph)C6H4}(m-H)] (13) (7 mg, 28%) h2-C6H3CH3)(m-H)(m-dppm)] (16) (8 mg, 31%) as colorless crystals
after recrystallization from hexane/CH2Cl2 at 4 C. The other three
bands gave minor unidentified products. Characterizing data for 15:
O O Anal. Calcd for C44H31O10Os3P3: C, 38.20; H, 2.26. Found: C, 38.43;
H, 2.33. IR (CH2Cl2): nCO ¼ 2055 s, 2031 s, 1998 s, 1980 s, 1957
Fu2P
Fu2P (CO)2 Ph sh cm1. 1H NMR (CDCl3, 25 C): aliphatic region: 15a: d ¼ 3.34 (q,
(CO)2 Ph 2
(OC)3 Os Os
2 (OC)3 Os Os P J ¼ 24.6, 12.4 Hz), 2.53 (q, J ¼ 24.6, 12.4 Hz); 15b: d ¼ 3.10 (q, J ¼ 24.0,
P
11.8 Hz), 2.73 (q, J ¼ 24.0, 11.8 Hz), aromatic region: 15aeb:
Os P Os P d ¼ 7.83e6.36 (m), hydride region: 15a: e17.31 (m); 15b: e17.27
(CO)2
(CO)2 H Ph2 H Ph2 (m). 31P{1H} NMR (CDCl3, 25 C): 15a: d ¼ 13.6 (dd, JPP ¼ 105.2,
203.2 Hz), 8.0 (d, JPP ¼ 105.2 Hz), e92.6 (d, JPP ¼ 203.2 Hz); 15b:
15b d ¼ 10.2 (dd, J ¼ 213.2, 98.8 Hz), 4.4 (d, J ¼ 98.8 Hz), 91.4 (d,
15a
JPP ¼ 213.2 Hz). ESI-MS: m/z ¼ 1383 [MþeH]. Characterizing data
Chart 2. for 16: Anal. Calcd for C47H35O9Os3P3: C, 40.11; H, 2.51. Found: C,
Table 1
Crystal data and structure refinement for the complexes [Os3(CO)8(PFu3){m3-Ph2PCH2P(Ph)C6H4}(m-H)] (5), [Os3(CO)9(PTh3)(m-dppm)] (7) and [Os3(CO)9(PPh3)(m-dppm)] (9).
[Os3(CO)8(PTh3)2(m-dppm)] (10), [Os3(CO)8(PFu3)2(m-dppm)] (12) and [Os3(CO)7(PTh3){m3-Ph2PCH2P(Ph)C6H4}(m-H)] (13). [Os3(CO)7(PPh3){m3-Ph2PCH2P(Ph)C6H4}(m-H)] (14),
[Os3(CO)7(m-PFu2)(m3-h2-C4H2O)(m-H)(m-dppm)] (15) and [Os3(CO)7(m-PFu2)(m3-h2-C6H3CH3)(m-H)(m-dppm)] (16).
5.CH2Cl2 7 9.0.5 CH2Cl2
Chemical formula C46H33Cl2O11Os3P3 C46H31O9Os3P3S3 C52.50H37.50ClO9Os3P3

Formula mass 1496.13 1487.40 1511.28
Crystal system Monoclinic Monoclinic Monoclinic
Space group P21/n C2/c C2/c
a [
A] 15.616(4) 40.680(5) 41.535(6)
b [
A] 20.069(5) 11.386(1) 11.645(2)
c [
A] 15.846(4) 19.890(2) 20.206(3)
a 90 90 90
b 102.479(4) 92.453(2) 92.990(2)
g 90 90 90
Cell volume [ A3] 4848(2) 9205(2) 9760(2)
Z 4 8 8
Calcd. density [g cm3] 2.050 2.147 2.057
Abs. coeff. m [mm1] 8.109 8.558 8.002
F(000) 2816 5600 5716
Crystal color Yellow Orange Orange
Crystal size [mm] 0.30 0.30 0.06 0.24 0.24 0.04 0.18 0.17 0.05
q range for data collection [ ] 2.62 to 28.29 2.75 to 28.30 2.29 to 28.31
Index ranges 19 h 20, 54 h 53, 55 h 53,
25 h 25, 15 h 15, 15 h 15,
20 h 20 26 h 26 26 h 26
Completeness to q 99.6% to 26.00 99.7% to 26.00 99.5% to 26.00
Reflections collected 40,924 39,109 40,686
Independent reflections 11,430 (Rint ¼ 0.0892) 10,997 (Rint ¼ 0.0521) 11,702 (Rint ¼ 0.0461)
Min. and max. transmission 0.1947 and 0.6418 0.2332 and 0.7259 0.3268 and 0.6904
Data/restraints/parameters 11,430/0/596 10,997/0/575 11,702/0/621
Final R indices [F2 > 2s] R1 ¼ 0.0484, R1 ¼ 0.0297, R1 ¼ 0.0308,
wR2 ¼ 0.1246 wR2 ¼ 0.0658 wR2 ¼ 0.0731
R indices (all data) R1 ¼ 0.0621, R1 ¼ 0.0367, R1 ¼ 0.0378,
wR2 ¼ 0.1320 wR2 ¼ 0.0683 wR2 ¼ 0.0757
Goodness-of-fit on F2 1.045 1.029 1.033
Largest diff. peak and hole [e.
A3] 4.254 and2.117 1.404 and1.431 1.803 and1.942
10.1.5 CH2Cl2 12.CH2Cl2.4H2O 13.CHCl3
Chemical formula C58.5H43Cl3O8Os3P4S6 C59H52Cl2O18Os3P4 C45H32Cl3O7Os3P3S3

Formula mass 1867.12 1814.39 1550.75
Crystal system Monoclinic Triclinic Monoclinic
Space group P21/n P 1 bar P21/c
a [
A] 23.143(4) 12.099(2) 13.424(4)
b [
A] 21.980(3) 15.578(2) 19.906(5)
c [
A] 24.468(4) 19.092(3) 18.093(5)
a 90 76.243(2) 90
b 98.651(2) 72.173(2) 90.885(4)
g 90 86.758(2) 90
Cell volume [ A3] 12,305(3) 3327.0(8) 4834(2)
Z 8 2 4
Abs. coeff. m [mm1] 6.672 5.957 8.309
F(000) 7144 1744 2920
Crystal color Orange Orange Red
Crystal size [mm] 0.46 0.16 0.13 0.42 0.12 0.04 0.46 0.42 0.12
Index ranges 30 h 30, 16 h 16, 17 h 17,
29 h 29, 20 h 20, 26 h 26,
32 h 31 24 h 24 23 h 24
Reflections collected 1,04,259 28,233 39,578
Independent reflections 29,564 (Rint ¼ 0.0498) 15,110 (Rint ¼ 0.0458) 11,407 (Rint ¼ 0.0740)
Data/restraints/parameters 29,564/0/1466 15,110/2/775 11,407/0/568
wR2 ¼ 0.1082 wR2 ¼ 0.1971 wR2 ¼ 0.1271
wR2 ¼ 0.1141 wR2 ¼ 0.2172 wR2 ¼ 0.1333
A3] 3.094 and1.768 4.738 and3.600 4.184 and1.884
14.1.5CH2Cl2 15 16.2CH2Cl2
Chemical formula C52H41Cl3O7Os3P3 C46H31O9Os3P3 C98H78Cl8O16Os6P6

Formula mass 1547.71 1391.22 3154.23
Crystal system Triclinic Triclinic Triclinic
Space group P 1 bar P 1 bar P 1 bar
Table 1 (continued )
14.1.5CH2Cl2 15 16.2CH2Cl2
a [
A] 10.487(2) 10.0797(6) 12.085(2)
b [
A] 15.456(3) 11.7563(7) 12.219(2)
c [
A] 16.719(3) 19.667(1) 38.384(6)
a 90.899(3) 79.920(1) 94.299(3)
b 99.824(3) 76.121(1) 92.388(3)
g 107.982(3) 67.817(1) 119.605(2)
Cell volume [ A3] 2533.0(8) 2085.8(2) 4894(1)
Z 2 2 2
Abs. coeff. m [mm1] 7.810 9.289 8.143
F(000) 1466 1304 2984
Crystal color Green Yellow Yellow
Crystal size [mm] 0.12 0.12 0.03 0.16 0.08 0.06 0.24 0.17 0.08
Index ranges 13 h 13, 13 h 12, 16 h 15,
20 h 19, 15 h 15, 16 h 16,
22 h 22 24 h 25 50 h 50
Reflections collected 21,849 17,296 41,880
Independent reflections 11,542 (Rint ¼ 0.0453) 9207 (Rint ¼ 0.0362) 22,249 (Rint ¼ 0.0344)
Data/restraints/parameters 11,542/0/603 9207/0/541 22,249/0/1204
wR2 ¼ 0.1011 wR2 ¼ 0.0718 wR2 ¼ 0.1378
wR2 ¼ 0.1233 wR2 ¼ 0.0780 wR2 ¼ 0.1545
A3] 2.035 and1.689 2.667 and2.297 2.405 and2.246
40.33; H, 2.56. IR (CH2Cl2): nCO ¼ 2061 s, 2032 s, 2008 s, 1987 s, 1971 oxygen atom has a short contact with a sulfur atom on a neigh-
s cm1. 1H NMR (CDCl3, 25 C): d ¼ 7.62 (m, 3H), 7.51 (m, 1H), 7.45 boring molecule [O(2)-S(10) 3.204 A]. Four carbon atoms in thienyl
(m, 3H), 7.23e7.03 (m, 13H), 6.97 (m, 2H), 6.83 (m, 2H), 6.74 (m, 1H), rings, namely C(27), C(47), C(59) and C(63), were refined only iso-
6.59 (m, 1H), 6.41 (m, 1H), 6.39 (m, 1H), 6.32 (m, 1H), 3.26 (dd, tropically. The asymmetric unit of 12 contains a disordered mole-
J ¼ 24.6, 12.4 Hz, 1H), 2.50 (dd, J ¼ 24.6, 12.4 Hz, 1H), 1.57 (s, 3H, cule of dichloromethane and four extra unconnected peaks in the
Me), 17.22 (dt, J ¼ 10.8, 7.6 Hz, 1H). 31P{1H} NMR (CDCl3, 25 C): difference map which have been modeled as oxygen atoms (pre-
d ¼ 19.2 (dd, JPP ¼ 111.6, 210.9 Hz, 1P), 5.8 (d, JPP ¼ 111.6 Hz, sumably from water). Hydrogen atoms were not placed on any of
1P), 98.0 (d, JPP ¼ 210.9 Hz, 1P). ESI-MS: m/z ¼ 1411 [MþeH]. these solvent molecules. The asymmetric unit of 13 contains a
disordered molecule of chloroform. Cluster 14 co-crystallized with
4.8. X-ray crystallography one and a half molecules of dichloromethane, the half molecule
being disordered over two sites. Both were refined only isotropi-
Single crystals of 5, 7, 9, 10, 13, 14, 15 and 16 suitable for X-ray cally and protons were not included for the disordered molecule.
structure analysis were grown by slow diffusion of hexane into For 16 there were two clusters and four molecules of dichloro-
dichloromethane solution at 4 C and that of 12 by slow diffusion of methane in the asymmetric unit. In one of the solvent molecules a
hexane into dichloroethane solution at 4 C. Diffraction intensities chlorine atom was equally disordered over two sites [Cl(8) and
were collected at 150(2) K with a Bruker SMART APEX2 CCD Cl(9)]. These atoms were refined only isotropically and protons
diffractometer using Mo-Ka radiation (l ¼ 0.71073 A). Indexing and were not generated. Scattering factors were taken from Interna-
initial cell refinements as well as the data collection were all done tional Tables for X-ray Crystallography [27]. Crystallographic data
using APEX2 [22] software. Data integration was accomplished are given in Table 1.
with SAINT [23] software and numerical absorption correction
(based on the real shape of the crystals) followed by scaling pro- 4.9. Computational methodology
cedure with SADABS program [24] were used to account for sys-
tematic effects. The structures were solved by direct methods [25] DFT calculations were performed with the Gassian09 package
and refined by full-matrix least squares [26]. In most of the struc- of programs [28]. The calculations were carried out with the
tures all non-hydrogen atoms were refined anisotropically and B3LYP functional, which utilizes the Becke three-parameter ex-
hydrogen atoms were included using a riding model. The structure change functional (B3) [29] combined with the correlation func-
of 5 contains a dichloromethane molecule in which one of the tional of Lee, Yang, and Parr (LYP) [30]. The osmium atoms were
chlorine atoms is disordered [Cl(2A)/Cl(2B)] and protons were not described by StuttgarteDresden effective core potentials (ecp)
generated for this. In 7, the sulfur-carbon atoms on one of the and an SDD basis set, while the 6e31G(d0 ) basis set was employed
thienyl groups are disordered over two sites. Cluster 9 co- for the remaining atoms. The geometry-optimized structures
crystallized with half a molecule of dichloromethane, the chlorine were drawn with the JIMP2 molecular visualization and manip-
atom of which makes a close contact (3.226 A) with one of the ulation program [31].
carbonyl oxygen atoms, O(3). For this complex, all hydrogen atoms
were located from difference maps and refined isotropically. The Acknowledgments
asymmetric unit of 10 contains two triosmium clusters and three
molecules of dichloromethane. There are short contacts of 2.87e This research has been partly sponsored by The Ministry of
3.05 A between oxygen atoms of the carbonyl ligands while one Education, Government of the Peoples Republic of Bangladesh. SG
thanks the Commonwealth Scholarship Commission for the award K. Hardcastle, J. Roe, V. Vazquez, C. Roe, S. Kabir, B. Roy, S. Alam, K.A. Azam,
Coord. Chem. Rev. 190-192 (1999) 975e1002;
of a Commonwealth Scholarship. GH thanks The Royal Society of
(c) Md.I. Hossain, S. Ghosh, G. Hogarth, G.M.G. Hossain, S.E. Kabir,
Chemistry for an International Authors Award which allowed him J. Organomet. Chem. 696 (2011) 3036e3039;
to complete this manuscript while visiting the University of North (d) A.K. Raha, Md.R. Hassan, S.E. Kabir, Md.M. Karim, B.K. Nicholson,
Texas. MGR acknowledges financial support from the Robert A. A. Sharmin, L. Salassa, E. Rosenberg, J. Clust. Sci. 19 (2008) 47e62;
(e) N. Begum, D.W. Bennett, G.M.G. Hossain, S.E. Kabir, A. Sharmin,
Welch Foundation (Grant B-1093) and the NSF (CHE-0741936). Prof. D.T. Haworth, T.A. Siddiquee, E. Rosenberg, J. Clust. Sci. 16 (2005) 413e428;
Michael B. Hall (TAMU) is thanked for providing us a copy of his (f) Md.A. Mottalib, N. Begum, S.M.T. Abedin, T. Akter, S.E. Kabir, Md.A. Miah,
JIMP2 program, which was used to prepare the geometry- D. Rokhsana, E. Rosenberg, G.M.G. Hossain, K.I. Hardcastle, Organometallics 24
(2005) 4747e4759;
optimized structures reported here. We also thank Ms. Anna (g) S. Ghosh, Md.R. Al-Mamun, G.M.G. Hossain, S.E. Kabir, Inorg. Chim. Acta
Gould who was supported by a Nuffield Foundation Undergraduate 378 (2011) 307e310;
Research Bursary for the VT NMR study of [Os3(CO)8(PTh3)2(m- (h) B. Bergman, R. Holmquist, R. Smith, E. Rosenberg, J. Ciurash, K. Hardcastle,
M. Visi, J. Am. Chem. Soc. 120 (1998) 12818e12828;
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Appendix A. Supplementary material ganometallics 17 (1998) 415e426;
(j) S.E. Kabir, H. Vahrenkamp, M.B. Hursthouse, K.M.A. Malik, J. Organomet.
Chem. 536e537 (1997) 509e517;
CCDC 941629, 941630, 941631, 941632, 941634, 941633, 941635, (k) S. Ghosh, Md.N. Uddin, N. Begum, G.M.G. Hossain, K.A. Azam, S.E. Kabir,
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(l) Kh.M. Uddin, S. Ghosh, A.K. Raha, G. Hogarth, E. Rosenberg, A. Sharmin,
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Journal of Organometallic Chemistry 751 (2014) 399e411

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Journal of Organometallic Chemistry

A comparative study of the reactivity of the lightly stabilized cluster

1. Introduction cluster [Os3(CO)8{m3-Ph2PCH2P(Ph)C6H4}(m-H)] (1) [11], ﬁrst prepared

Fig. 3. ORTEP diagram of the molecular structure of [Os3(CO)9(PPh3)(m-dppm)] (9),

thermodynamically less stable isomer 10b forms is far from clear.

4.6. Thermolysis of [Os3(CO)8(PPh3)2(m-dppm)] (11)

5.CH2Cl2 7 9.0.5 CH2Cl2

Chemical formula C46H33Cl2O11Os3P3 C46H31O9Os3P3S3 C52.50H37.50ClO9Os3P3

10.1.5 CH2Cl2 12.CH2Cl2.4H2O 13.CHCl3

Chemical formula C58.5H43Cl3O8Os3P4S6 C59H52Cl2O18Os3P4 C45H32Cl3O7Os3P3S3

Chemical formula C52H41Cl3O7Os3P3 C46H31O9Os3P3 C98H78Cl8O16Os6P6

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