Inorganica Chimica Acta 409 (2014) 320–329

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Inorganica Chimica Acta

journal homepage: www.elsevier.com/locate/ica

Bimetallic osmium-tin complexes: Stannylene and hydrostannylene

clusters upon addition of Ph3SnH to unsaturated triosmium clusters
[(l-H)2Os3(CO)8(l-diphosphine)] (diphosphine = dppm, dppf)
Jagodish C. Sarker a, Kh. Mahid Uddin a, Md. Saifur Rahman a, Shishir Ghosh a, Tasneem A. Siddiquee c,
Derek A. Tocher b, Michael G. Richmond 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, Tennessee State University, 3500 John A. Merritt Blvd., Nashville, TN 37209, USA
d
Department of Chemistry, University of North Texas, 1155 Union Circle, Box 305070, Denton, TX 76203, USA

a r t i c l e i n f o a b s t r a c t

Article history: Products of the addition of Ph3SnH to the unsaturated triosmium clusters [(l-H)2Os3(CO)8(l-dppm)] (1)
Received 29 July 2013 and [(l-H)2Os3(CO)8(l-dppf)] (2) are highly dependent on the nature of the diphosphine. With the rigid
Received in revised form 10 September bis(diphenylphosphino)methane (dppm), the stannylene complex [H2Os3(CO)7(l-SnPh2)2(l-dppm)] (3)
2013
is the major cluster product (35% yield), resulting from both Sn–H and Sn–C bond activation, while
Accepted 13 September 2013
Available online 21 September 2013
two previously reported triphenyltin complexes, [(l-H)2Os3(CO)8(SnPh3)2(l-dppm)] (4) (10% yield) and
[(l-H)2Os3(CO)8(SnPh3){l-Ph2PCH2P(Ph)C6H4}] (5) (11% yield) also result. Biphenyl is also a co-product
of this reaction and it is postulated to be formed concomitantly with 3. A similar reaction with the
Keywords:
Osmium cluster
highly flexible 1,10 -bis(diphenylphosphino)ferrocene (dppf) complex leads to the formation of four
Diphosphine tin-containing complexes: two previously reported compounds [HOs(CO)4(SnPh3)] (6) (8% yield) and
Hydride [Os2(CO)6(SnPh3)2(l-SnPh2)2] (8) (5% yield), and the new triphenyltin and hydrostannylene clusters
Triphenyltin hydride [H(l-H)2Os3(CO)8(SnPh3)(l-dppf)] (10) (22% yield) and [(l-H)Os2(CO)4(SnPh3)2(l-HSnPh2)(l-dppf)] (9)
Crystal structure (12% yield) respectively, together with the dihydroxy cluster [Os3(CO)8(l-OH)2(l-dppf)] (7). Two of these
DFT new clusters have been characterized by X-ray crystallography. Cluster 3 consists of a central Os3 triangle
with two stannylene groups, each bridging one Os–Os edge, a dppm ligand that bridges the third Os-Os
edge, and two terminal hydride ligands. Cluster 10 consists of an Os3 triangle with a terminal SnPh3
group, one terminal and two bridging hydride ligands, and a bridging dppf ligand. The new compounds
3, 7, 9, and 10 have been investigated by electronic structure calculations, and the computed ground-
state structures are discussed relative to the X-ray crystallographic structures.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction the chemistry of transition metal-tin compounds [27–30], since

tin is often used as a modifier in bimetallic catalysts because its
During the past three decades the synthesis and reactivity of presence has been shown to lead to enhanced product selectivity
transition metal complexes bearing diphosphine ligands has at- in a variety of chemical transformations [31–40]. Additionally,
tracted considerable attention because of their ability to promote there is strong evidence that tin can assist in the binding of metal-
organic transformations [1], their aptitude to act as templates for lic nanoparticles to oxide supports of heterogeneous catalysts
the synthesis of metal–metal bonds by bridge-assisted reactions [34–41]. Group 14 metals can be incorporated into transition-me-
[2–6], and their versatile application in homogeneous catalysis tal clusters in a number of ways [42] and using these methods a
[7–11]. This versatility is highly prominent in the case of the flex- number of osmium-tin clusters have been prepared [43]. For
ible diphosphine, 1,10 -bis(diphenylphosphino)ferrocene (dppf) example, oxidative-addition of R3M0 H (M0 = Ge, Sn; R = Me, Et, Bu,
[12–18], due to its ability to adopt various coordination modes that Ph) to the labile complexes [M3(CO)12n(CH3CN)n] (M = Os, Ru;
can match the steric requirements of the molecular environment n = 1, 2) gives mixed-metal clusters of the type [(l-H)M3(CO)11
during catalysis [19–26]. Presently, there is extensive interest in (M0 R3)] and [(l-H)M3(CO)10(CH3CN)(M’R3)] [44], while a similar
oxidative-addition of R3EH (E = Si, Sn; R = Et, Bu, Ph) at the unsat-
urated cluster [(l-H)2Os3(CO)10] furnishes [(l-H)3Os3(CO)10(ER3)]
⇑ Corresponding authors. [45]. Cleavage of one or more phenyl groups from the ER3 moiety
E-mail address: [email protected] (S.E. Kabir).

0020-1693/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ica.2013.09.021
 J.C. Sarker et al. / Inorganica Chimica Acta 409 (2014) 320–329 321

is an important transformation that is mediated by these metal [(l-H)2Os3(CO)8(l-dppm)] (1) [51] and [(l-H)2Os3(CO)8(l-dppf)]
complexes and can lead to catalyst deactivation during autoge- (2) [52] were prepared according to published procedures. IR spec-
neous catalysis. Adams et al. [46–49] have reported that reactions tra were recorded on a Schimadzu FTIR-8101 spectrophotometer,
of Ph3SnH with metal carbonyl clusters can lead to the formation of and the 1H and 31P{1H} NMR spectra were recorded on a Bruker-
polynuclear complexes containing l-SnPh2 (stannylene), l3-SnPh VNMRS 400 MHz spectrometer. All chemical shifts are reported
or l4-Sn ligands due to the cleavage of a phenyl group(s) from in d units and are referenced to the residual protons of the deuter-
the intermediate Ph3Sn-substituted clusters. The resulting clus- ated solvents and external H3PO4 (85%) for the 1H and 31P chemical
ter-bound phenyl group is not generally stable under the reaction shifts, respectively. Elemental analyses were performed by the
conditions and typically undergoes reductive-elimination to afford microanalytical laboratory of Wazed Miah Science Research Centre
benzene as a by-product. at Jahangirnagar University.
We recently published details on the synthesis and structural
characterization of the bimetallic Os–Sn complexes [(l-H)2Os3 2.1. Reaction of [(l-H)2Os3(CO)8(l-dppm)] (1) with Ph3SnH
(CO)8{l3-Ph2PCH2P(Ph)C6H4}(SnPh3)] and [(l-H)2Os3(CO)8(l-dppm)
(SnPh3)2], which are formed upon reaction of the lightly stabilized To a toluene solution (20 mL) of 1 (50 mg, 0.042 mmol) was
cluster [(l -H)Os 3 (CO) 8 { l3 -Ph2 PCH 2 P(Ph)C6 H 4 }] with Ph3 SnH added Ph3SnH (35 mg, 0.10 mmol) and the mixture was refluxed
(Scheme 1) [50,51]. The stepwise activation of Ph3 SnH at for 1.5 h, during which time the colour changed from red to yellow.
[(l-H)Os3(CO)8{l3-Ph2PCH2P(Ph)C6H4}] occurs at room tempera- The solvent was removed under reduced pressure and the residue
ture to initially furnish [(l-H)2Os3(CO)8{l3-Ph2PCH2P(Ph)C6H4} separated by TLC on silica gel. Elution with hexane/CH2Cl2 (3:2,
(SnPh3)], followed by the subsequent formation of [(l-H)2Os3 v/v) developed five bands. The first band was biphenyl (2 mg, 31%)
(CO)8(l-dppm)(SnPh3)2], in which the two Ph3Sn ligands are situ- and the second band gave unconsumed 1 (trace). The third band
ated at adjacent osmium centers (1,2-substitution). The latter is afforded [H2Os3(CO)7(l-SnPh2)2(l-dppm)] (3) (25 mg, 35%) as
the product of kinetic control and undergoes isomerization to the yellow crystals after recrystallization from hexane/CH2Cl2 at 4 °C,
corresponding 1,1-substituted isomer (both Ph3Sn ligands at the and the fourth and fifth bands gave the previously reported
same osmium center) at elevated temperatures. Thus, reaction of [(l-H)2Os3(CO)8(SnPh3)2(l-dppm)] (4) (8 mg, 10%) and [(l-H)2Os3
[(l-H)Os3(CO)8{l3-Ph2PCH2P(Ph)C6H4}] with two equivalents of (CO)8(SnPh3){l-Ph2PCH2P(Ph)C6H4}] (5) (7 mg, 11%), respectively
Ph3SnH under more vigorous conditions yields the thermodynam- [50]. Analytical and spectral data for 3: Anal. Calc. for C56H44O7Os3
ically stable isomer [(l-H)2Os3(CO)8(l-dppm)(SnPh3)2] as the sole P2Sn2: C, 39.59; H, 2.61; Found: C, 39.77; H, 2.68%. IR (mCO,
product. Seeking to extend our studies on the synthesis of new CH2Cl2): 2066(w), 2020(m), 1987(vs), 1969(m), 1939(m) cm1.
tin-containing osmium clusters, we have now investigated the 1
H NMR (CD2Cl2): d 10.54 (d, JH–P = 15.5 Hz, 2H), 3.88 (m, 2H),
reactions of the diphosphine-substituted unsaturated clusters 7.30 (m, 20H), 7.58 (m, 10H), 7.74 (m, 10H). 31P{1H} NMR (CD2Cl2):
[(l-H)2Os3(CO)8(l-dppm)] (1) and [(l-H)2Os3(CO)8(l-dppf)] (2) d 17.45 (s).
with Ph3SnH and report here that the outcome of these reactions
is highly dependent upon the nature of the diphosphine and leads
2.2. Reaction of [(l-H)2Os3(CO)8(l-dppf)] (2) with Ph3SnH
to a range of triphenyltin- and diphenylstannylene and hydrost-
annylene-containing products.
Analogous to the reaction described above, 2 (50 mg,
0.037 mmol) and Ph3SnH (30 mg, 0.085 mmol) were heated in
2. Experimental details refluxing toluene for 4.5 h, after which time the solvent was
removed under vacuum and the residue purified by chromato-
All reactions were carried out under a nitrogen atmosphere graphic separation. Six bands were isolated in order of elution
using standard Schlenk techniques and solvents were dried and being found to be; biphenyl (trace), [HOs(CO)4(SnPh3)] (6) (2 mg,
distilled prior to use by standard methods. The compounds dppm, 8%), [Os3(CO)8(l-OH)2(l-dppf)] (7) (4 mg, 8%), [Os2(CO)6(SnPh3)2
dppf and Ph3SnH were purchased from Acros Chemicals Inc. and (l-SnPh2)2] (8) (3 mg, 5%), [(l-H)Os2(CO)4(SnPh3)2(l-HSnPh2)
used without further purification. The triosmium clusters (l-dppf)] (9) (9 mg, 12%), and [H(l-H)2Os3(CO)8(SnPh3)(l-dppf)]

Ph Ph
P P

Ph2 P Ph3SnH Ph2P

Os(CO)3 (OC)3 Os Os(CO)3
(OC)3 Os
25 oC H
H Os H Os
(CO)2 Ph3Sn (CO)2

xs Ph3SnH 128 oC Ph3SnH 25 oC

Ph3Sn
H (CO)3 Ph2 (CO)3 H (CO)3 Ph2
(OC)2Os Os P 128 oC Os Os P
Ph3Sn
H Os P Os P
Ph3Sn (CO)3 Ph2 H
(CO)2 Ph2
Ph3Sn
4

Scheme 1.
322 J.C. Sarker et al. / Inorganica Chimica Acta 409 (2014) 320–329

(10) (14 mg, 22%). Analytical and spectral data for 7: Anal. Calc. for out the absorption corrections. The structures were solved using
C42H30FeO10Os3P2: C, 36.47; H, 2.19; Found: C, 36.62; H, 2.32%. IR the Patterson method and difference Fourier techniques (SHELXTL,
(mCO, CH2Cl2): 2063(s), 2008(vs), 1989(s), 1962(s) cm1. 1H NMR V6.12) [56]. With the exception of the hydride ligands in 10 that
(CD2Cl2): d 0.37 (t, JH–P = 4.7 Hz, 2H), 4.13 (m, 4H), 4.85 (m, 4H), could not be crystallographically located, all other hydrogen atoms
7.50 (m, 20H). 31P{1H} NMR (CD2Cl2) d 3.15. Analytical and spectral were placed in their expected chemical positions using the HFIX
data for 9: Anal. Calc. for C88H70FeO6Os2P2Sn3: C, 50.87; H, 3.40; command and allowed to ride on the appropriate heavy atom dur-
Found: C, 51.04; H, 3.57%. IR (mCO, CH2Cl2): 2014(m), 1972(vs), ing data refinement. Scattering factors and anomalous dispersion
1923(m) cm-1. 1H NMR (CD2Cl2): d 16.38 (dd, JH–P = 14.0, 8.0 Hz, corrections are taken from the International Tables for X-ray crys-
1H), 11.25 (d, JH-P = 10.7 Hz, 1H), 4.08 (m, 4H), 4.28 (m, 4H), tallography.[57] Structure solution, refinement, graphics, and gen-
6.85 (m, 17H), 6.94 (m, 13H), 7.02 (m, 11H), 7.14 (m, 4H), 7.25 eration of publication materials were performed by using SHELXTL,
(m, 3H), 7.40 (m, 12H). 31P{1H} NMR (CD2Cl2) d 15.96 (t, JSn–P = V6.12 software. Additional details pertaining to the data collection
42.5 Hz, 1P), 9.75 (t, JSn–P = 28.2 Hz, 1P). Analytical and spectral and structure refinement are given in Table 1, with selected bond
data for 10: Anal. Calc. for C60H46FeO8Os3P2Sn: C, 42.34; H, 2.72; distances and angles reported in Table 2.
Found: C, 42.60; H, 2.87%. IR (mCO, CH2Cl2): 2080(w), 2042(w),
1999(vs), 1960(sh) cm1. 1H NMR (CD2Cl2): (major isomer)
2.4. Computational methodology and modeling details
d 19.37 (d, JH–P = 22.8 Hz, 1H), 18.64 (br s, 1H), 8.66 (br s,
1H), 4.12 (m, 8H), 7.40 (m, 33H), 8.00 (m, 2H); (minor isomer)
All calculations were performed with the hybrid DFT functional
d 17.30 (d, JH-P = 22.8 Hz, 1H), 15.91 (m, 1H), 10.22 (m, 1H),
B3LYP, as implemented by the GAUSSIAN 09 program package [58].
4.12 (m, 8H), 7.40 (m, 33H), 8.00 (m, 2H). 31P{1H} NMR (CD2Cl2):
This functional utilizes the Becke three-parameter exchange func-
(major isomer) d 8.15 (s, 1P), 2.70(s, 1P); (minor isomer)
tional (B3) [59], combined with the correlation functional of Lee,
d 11.20 (s, 1P), 5.0(s, 1P).
Yang and Parr (LYP) [60]. The Sn, Os, and Fe atoms were described
by Stuttgart-Dresden effective core potentials (ecp) and a SDD basis
2.3. X-ray structure determination set, while the 6-31G(d0 ) basis set, as implemented in the Gaussian
09 program suite, was employed for the remaining atoms. The ini-
Single crystals of 3 and 10 suitable for X-ray diffraction were tial coordinates for compounds 3, 7, 9, and 10 were taken from the
grown by slow diffusion of hexane into a dichloromethane solution available X-ray data and for those structures whose hydrides were
containing each cluster at 4 °C. The selected crystals were coated not crystallographically located, the missing atoms were added to
with Paratone-N oil and mounted on a glass fibre (3) or suspended the appropriate locus. In the case of 9 that contained 170 atoms,
in a small fiber loop (10), and the diffraction data were collected in the phenyl groups were replaced with methyl groups in order to
a cooled nitrogen gas stream at 123 K (3) and 150 K (10). All data facilitate the geometry optimization. The reported ground-state
were collected on a Bruker D8 SMART APEX CCD sealed-tube diffrac- geometries were fully optimized and the analytical Hessian affor-
tometer with graphite monochromated Mo Ka radiation ded only positive eigenvalues. The natural charges and Wiberg
(k = 0.71073 Å). Data collection, indexing, and initial cell refine- bond indices reported here were computed using Weinhold’s natu-
ments were all carried out using SMART software [53]. The frame ral bond orbital (NBO) program, as executed by GAUSSIAN 09 [61,62].
integration and final cell refinements were carried out using SAINT The geometry-optimized structures have been drawn with the
software [54], while the SADABS [55] program was used to carry JIMP2 molecular visualization and manipulation program [63].

Table 1
Crystallographic Data and Structure Refinement for compounds 3 and 10.

Compound 3 10
Empirical formula C56H44O7Os3P2Sn2 C60H48FeO8Os3P2Sn
Formula weight 1698.6 1704.20
Temp (K) 123(2) 150(2)
Wavelength (Å) 0.71073 0.71073
Crystal system monoclinic triclinic
Space group P2l/c P1
a (Å) 22.421(4) 12.532(1)
b (Å) 12.296(2) 14.028(1)
c (Å) 19.578(3) 17.595(2)
a (°) 90 95.617(1)
b (°) 101.438(3) 105.407(1)
c (°) 90 98.669(1)
V (Å3) 5290(1) 2916.8(4)
Z 4 2
Dcalc (Mg m3) 2.130 2.051
l (Mo Ka) (mm1) 8.222 7.377
F(0 0 0) 3168 1708
Crystal size (mm3) 0.21  0.08  0.06 0.28  0.24  0.06
h (°) 2.26–28.28 2.66–28.27
Index ranges 29 6 h 6 29, 16 6 k 6 15, 25 6 l 6 25 16 6 h 6 16, 18 6 k 6 18, 23 6 l 6 23
Reflections collected 43713 24895
Independent reflections (Rint) 12334 (0.0665) 13234 (0.0321)
Max. and min. transmission 0.2771 and 0.6383 0.2319 and 0.6659
Data/restraints/parameters 12334/0/631 13234/0/707
Goodness-of-fit on F2 0.946 1.065
Final R indices [I > 2r(I)] R1 = 0.0409, wR2 = 0.0818 R1 = 0.0417, wR2 = 0.1059
R indices (all data) R1 = 0.0691, wR2 = 0.0935 R1 = 0.0484, wR2 = 0.1160
Largest difference in peak and hole (e Å3) 2.233 and 1.643 7.018 and 4.202
 J.C. Sarker et al. / Inorganica Chimica Acta 409 (2014) 320–329 323

Table 2 3. Results and discussion

Selected bond distances (Å) and angles (°) for compounds 3 and 10.

Diffraction data DFT data 3.1. Reaction of [(l-H)2Os3(CO)8(l-dppm)] (1) with Ph3SnH
Compound 3
Bond distances Reaction of unsaturated 1 with excess Ph3SnH in refluxing
Os(1)–Os(2) 2.9301(5) 3.0236 toluene afforded the electron-precise distannylene dihydride clus-
Os(1)–Os(3) 2.9316(5) 3.0599
ter [H2Os3(CO)7(l-SnPh2)2(l-dppm)] (3) in 35% yield (Scheme 2),
Os(2)–Os(3) 2.9668(5) 3.0696
Os(2)–P(1) 2.317(2) 2.373 together with the previously reported compounds [(l-H)2Os3
Os(1)–P(2) 2.308(2) 2.365 (CO) 8 (SnPh 3 ) 2 ( l -dppm)] (4) and [( l -H) 2 Os 3 (CO) 8 (SnPh 3 )
Os(1)–Sn(1) 2.6197(6) 2.714 {l-Ph2PCH2P(Ph)C6H4}] (5) (Scheme 1) in 10% and 11% yields
Os(2)–Sn(2) 2.6441(6) 2.715 respectively [50]. Biphenyl was obtained as a co-product from this
Os(3)–Sn(2) 2.6691(6) 2.743
reaction in a yield (31%) comparable to that found for 3, suggesting
Os(3)–Sn(1) 2.6864(6) 2.742
Os(1)–H(terminal) 1.66 that the organic co-product and 3 possibly originate from a com-
Os(2)–H(terminal) 1.66 mon intermediate that is unstable under the thermolysis reaction.
Bond angles Cluster 3 has been fully characterized by IR and NMR spectrosco-
P(2)–Os(1)–Sn(1) 150.44(4) 152.21 pies and single crystal X-ray diffraction analysis. It is closely
Sn(1)–Os(1)–Os(2) 118.31(1) 116.71 related to the reportedly electron-precise paramagnetic cluster
Sn(1)–Os(1)–Os(3) 57.56(2) 56.33
[Os3(CO)8(l-SnR2)2(l-dppm)] [R = CH(SiMe3)2], published earlier
P(2)–Os(1)–Os(2) 91.25(4) 91.08
P(2)–Os(1)–Os(3) 151.97(4) 151.17
by Cardin and co-workers [64], and the diamagnetic ruthenium
P(1)–Os(2)–Sn(2) 150.97(4) 151.14 complex [Ru3(CO)8(l-SnAr2)2(l-dppm)] [Ar = 2,4,6-Pri3Ph] [65].
Sn(2)–Os(2)–Os(1) 115.73(1) 116.29 An ORTEP diagram of the molecular structure of 3 is depicted in
P(1)–Os(2)–Os(1) 93.30(4) 92.55 Fig. 1. The structure consists of an equilateral triangle of
P(1)–Os(2)–Os(3) 152.09(4) 152.21
osmium atoms with three elongated and approximately equal
Sn(1)–Os(3)–Os(1) 55.38(1) 55.45
Sn(2)–Os(3)–Os(2) 55.65(1) 55.34 Os–Os bond lengths [Os(1)–Os(2) 2.9303(5), Os(1)–Os(3)
Os(2)–Sn(2)–Os(3) 67.89(1) 68.44 2.9317(5), Os(2)–Os(3) 2.9669(5) Å]. These are comparable to the
P(2)–C(8)–P(1) 117.4(3) 117.7 Os–Os distances in [Os3(CO)9(l-SnPh2)3] [Os–Os = 2.9629(4),
Sn(2)–Os(3)–Sn(1) 169.77(2) 169.70
2.9572(4), 2.9906(4) Å] [49] but significantly different from those
Sn(2)–Os(3)–Os(1) 114.89(1) 114.25
Sn(1)–Os(3)–Os(2) 114.90(1) 114.36
in [Os3(CO)8(l-SnR2)2(l-dppm)] [where R = CH(SiMe3)2; Os–Os =
3.048(2), 2.854(2), 2.909(2) Å] [64]. The Os(3) center has three
Compound 10
Bond distances
terminal carbonyls, while the Os(1) and Os(2) centers each bind
Os(1)–Os(3) 2.9038(4) 2.9903 two. The two hydrides were crystallographically located and found
Os(1)–Sn(1) 2.6647(6) 2.7678 to be terminally bonded to the Os(1) and Os(2) centers; the calcu-
Os(1)–Os(2) 3.0525(4) 3.2200 lated DFT structure corroborates the positioning of the ancillary
Os(2)–Os(3) 3.0977(5) 3.2549
ligands about the metallic core. In comparison to the multitude of
Os(3)–P(2) 2.356(2) 2.431
Os(2)–P(1) 2.341(2) 2.404 polynuclear clusters that contain an edge-bridging or face-capping
Os(2)-H(terminal) 1.67 hydride(s), cluster examples possessing terminal hydride(s) are
Os(3)-H(a) 1.82 relatively few in number [66]. The Os(1)–Os(2) edge is bridged by
Os(2)-H(a) 1.87
the dppm, and the two bridging diphenlstannylene groups each
Os(2)-H(b) 1.80
Os(1)-H(b) 1.81
ligating one of the two remaining Os–Os edges. The four Os–Sn
Sn(1)-H(b) 3.11 bond distances [Os(1)–Sn(1) 2.6197(6), Os(3)–Sn(1) 2.6865(6),
Bond angles
Os(2)–Sn(2) 2.6441(6), Os(3)–Sn(2) 2.6694(6) Å] are comparable
C(1)–Os(1)–Sn(1) 92.1(2) 87.4 to those in [Os3(CO)9(l-SnPh2)3] [49]. The osmium-phosphorus
P(1)–Os(2)–Os(1) 161.45(5) 163.29 bond distances [Os(2)–P(1) 2.317(2), Os(1)–P(2) 2.308(2)] are unre-
Os(3)–Os(1)–Os(2) 62.61(1) 63.09 markable in comparison to those in [(l-H)2Os3(CO)8(l-dppm)].[67]
Os(1)–Os(2)–Os(3) 56.343(9) 55.007
Cluster 3 is electron-precise and exhibits a 48e count, assuming the
P(2)–Os(3)–Os(1) 173.00(4) 169.73
P(2)–Os(3)–Os(2) 122.77(4) 117.70 two bridging stannylene ligands function as 2e donor ligands.
Sn(1)–Os(1)–Os(3) 160.93(2) 167.71 Spectroscopic data for 3 are consistent with the solid-state
Sn(1)–Os(1)–Os(2) 101.71(2) 107.20 structure. The IR spectrum exhibits five m(CO) absorption bands
P(1)–Os(2)–Os(3) 109.43(5) 113.18
in the region 2066–1939 cm1 in agreement with the presence of
Os(1)–Os(3)–Os(2) 61.044(9) 61.904
Os(3)–Os(2)–H(terminal) 80.43
terminally coordinated carbonyl ligands. The 1H NMR spectrum
Os(1)–Os(2)–H(terminal) 77.24 shows the expected phenyl hydrogens as three distinct groups be-
Os(3)–H(a)–Os(2) 123.34 tween d 7.30–7.74, while the methylene hydrogens of the dppm
Os(2)–H(b)–Os1(1) 126.33 appear as a multiplet centered at d 3.88. The high-field doublet
at d 10.54, which integrates for 2H, is readily assigned to the

(CO)3
Os
H (CO) Ph Ph2Sn SnPh2
2 2
(OC)4Os Os P Ph3SnH H
Os Os
H + 4 + 5
(CO)2 Os P (CO)2 (CO)2
Ph2 110 oC
H Ph2P PPh2
- Ph-Ph
1
3

Scheme 2.
324 J.C. Sarker et al. / Inorganica Chimica Acta 409 (2014) 320–329

Fig. 1. ORTEP diagram of the molecular structure of [H2Os3(CO)8(l-SnPh2)2(l-dppm)] (3) at the 50% probability level (left) and the DFT-optimized structure of 3 (right).

H
O (CO) Ph
CO 2 2 Ph2
CO (OC)4Os Os P Ph3Sn Sn
H Os CO X (CO)3
(CO)2 Os P + Os Os
Ph3Sn + Ph2 (CO)3
O Sn SnPh3
CO Ph2
H
H
(CO)2 Ph2 6 7 8
(OC)4Os Os P Ph3SnH
X
(CO)2 Os P 110 oC
Ph2 H (CO) SnPh3 Ph3Sn H
H 2 Ph2 (CO)2
X = (C5H4)2Fe Ph2Sn Os P Os Os PPh2
2 X + (CO)3 H
Ph3Sn Os P Os X
P
(CO)2 H Ph2 (CO)3
H HPh 2

9 10

Scheme 3.

two terminal hydrides, the observed doublet pattern arising from Characterization of 7 by X-ray diffraction analysis was at-
geminal coupling with one phosphorus atom of the dppm ligand. tempted, but the crystals were of poor quality and contained a
Finally, the 31P{H} NMR spectrum displays a singlet at d 17.45, number of disordered atoms. While attempts to grow high quality
implying that 3 contains equivalent phosphorus nuclei in solution crystals were not successful, a preliminary diffraction structure
as a result of the symmetrical coordination of the diphosphine and confirmed the presence of an Os3 cluster that contained a bridging
the other ancillary ligands about the cluster polyhedron. dppf ligand, in addition to a pair of bridging hydroxyl groups asso-
ciated with the two Os centers ligated by the dppf ligand. The
3.2. Reaction of [(l-H)2Os3(CO)8(l-dppf)] (2) with Ph3SnH geometry-optimized structure for 7 was computed (Fig. 2) and
found to be in agreement with the crude diffraction structure
The reaction of 2 with Ph3SnH does not parallel that with 1. Un- and the related hydroxyl- and alkoxide-substituted clusters
der similar conditions the dppf-substituted cluster 2 reacts with [Ru3(CO)8(l-OH)2(l-dppf)] [52], [Ru3(CO)8(l-OH)2(l-BINAP)]
excess Ph3SnH to give four tin-containing complexes, namely the [69], [Os3(CO)10n(EPh3)n(l-OR)2] (R = H, Me, Et; n = 1, 2) [70]
new clusters [(l-H)Os2(CO)4(SnPh3)2(l-HSnPh2)(l-dppf)] (9) and and [Os3(CO)10(l-OH)(l-OMe)] [71]. The computed internuclear
[H(l-H)2Os3(CO)8(SnPh3)(l-dppf)] (10) in 12 and 22% yields, Os1  Os2 distance of 3.2020 Å and the Os(1)–O(1,2)–Os(2) angles
respectively, along with the known complexes [Os2(CO)6(SnPh3)2 of 94° support the elongation of the metallic edge that is bridged
(l-SnPh2)2] (8) and [HOs(CO)4(SnPh3)] (6) in 5% and 8% yields, by the dppf and hydroxyl ligands. The presence of two formal
respectively [68]. A fifth product, [Os3(CO)8(l-OH)2(l-dppf)] (7) Os–Os bonds in 7 is also reflected in the computed Wiberg indices,
(8% yield) contains no tin (Scheme 3). The new clusters 7, 9, and which are reported in Table 3. The Os2–Os3 and Os1–Os3 vectors
10 have been characterized by a combination of spectroscopic each exhibit a value of 0.45, and this magnitude is indicative of
techniques and single crystal X-ray diffraction analyses. an Os-Os single bond [72]. The smaller Wiberg index of 0.11 for
 J.C. Sarker et al. / Inorganica Chimica Acta 409 (2014) 320–329 325

computed at each osmium center reveals that 9-Me is the most

electron-rich of the osmium-tin compounds investigated in this re-
port. The Wiberg bond index of 0.22 for the hydride-bridged Os(1)–
Os(2) vector is approximately 50% of that found for the Os-Os
bonds in 3 and 7, and other triosmium clusters examined by us
[72]. The hydride-bridged Os(2)–Sn(1) bond in 9-Me also displays
a similar reduction in its bond order, viz-à-viz the three other Os–
Sn bonds that display a mean Wiberg index of 0.65. The hydride
that spans the Os(2)–Sn(1) vector in 9-Me is more strongly bound
to the osmium center based on the reported Wiberg indices in
Table 3, and it does not interact significantly with the tin center
of the promixal Ph3Sn moiety based on a Wiberg index of 0.05.
Cluster 9-Me contains 34 valence electrons and is coordinatively
saturated, assuming that the Ph3Sn and hydride ligand serve as
one-electron donors and the hydrostannyl-bridge functions as a
three-electron donor. The computed Os–Os distance of 3.36 Å is
considerably longer than the Os–Os distance in 8 [3.1471(2) Å],
and this phenomenon is likely due to the composite lengthening
effect known to be promoted by both bridging hydride and
hydrostannylene ligands [66,73].
Consistent with the formulated structure of 9, the 1H NMR spec-
trum exhibits a doublet at d 11.25 (JPH = 10.7 Hz) and a doublet of
doublets at d 16.38 (JPH = 14.0, 10.0 Hz). The former is assigned to
Fig. 2. DFT-optimized structure of 7. the hydride that spans the Os–Sn vector associated with the Os2Sn
polyhedral core while the latter to the hydride that bridges the
two osmium centers. The 31P{1H} NMR spectrum shows two
the Os1 and Os2 centers is in keeping with the reduced bond order singlets with tin satellites at 15.96 (JSn–P = 42.5 Hz) and 9.75
of this vector, which is directly influenced by the electron donation (JSn–P = 28.2 Hz) ppm consistent with the inequivalent phosphorus
from the ancillary ligands at these two osmium centers. Cluster 7 groups, as revealed in the crude X-ray structure. A number of
contains 50 valence electrons and may be viewed as having seven related hydrostannyl-bridged complexes have previously been
skeletal electron pairs (SEP), assuming that the two bridging hy- reported; [74,75] most closely related to 9 is the triosmium cluster
droxyl groups function as 3e donor ligands. Consequently, 7 only [(l-H)Os3(CO)10(l-HSnR2)] [R = CH(SiMe3)2] that is formed upon
contains two Os–Os bonds. addition of free stannylene SnR2 to [(l-H)2Os3(CO)10] [75].
Spectroscopic data for 7 are consistent with the DFT structure. An ORTEP diagram of 10 is depicted in Fig. 4 with the DFT struc-
The m(CO) region of the IR spectrum is akin to that of [Ru3(CO)8 ture positioned alongside for comparison. The structure consists of
(l-OH)2(l-dppf)], suggesting a similar distribution of carbonyls a triangular array of osmium atoms with two significantly elon-
[52]. In addition to the phenyl proton resonances, the 1H NMR gated and approximately equal metal-metal bonds [Os(1)–
spectrum shows two multiplets at d 4.13 and 4.85, each integrating Os(2) = 3.0525(4), Os(2)–Os(3) = 3.0977(5) Å] and one compara-
to 4H due to the cyclopentadienyl protons and an upfield triplet at tively shorter [Os(1)–Os(3) = 2.9038(4)] edge. The SnPh3 group is
d 0.37 that is assigned to the two hydroxyl protons. The latter equatorially coordinated to Os(1), and the Os(1)–Sn(1) bond dis-
hydrogen atoms appear as a triplet due to vicinal coupling to the tance of 2.6647(6) Å is comparable to that of 2.6664(3) Å found
two phosphine moieties (JPH = 4.7 Hz), and the chemical shift and in [(l-H)Os3(CO)9(SnPh3)(l-dppm)] [50]. The hydrides in 10 could
the coupling data are comparable to the NMR data previously re- not be crystallographically located, but two of the three were as-
ported by us for the ruthenium analogue [52]. The 31P{1H} NMR sumed to span to Os(1)–Os(2) and Os(2)–Os(3) vectors [73]. The li-
spectrum displays a singlet at 3.15 ppm, confirming the equiva- gand distribution and the ‘‘empty’’ coordination site at Os(2)
lence of the two phosphorus nuclei in solution. suggest that the remaining hydride is terminally bound to the
The initial characterization of 9 was made by X-ray crystallog- Os(2) center. The locus of all three hydrides was verified by DFT
raphy. Here we were able to grow single crystals of 9 but the crys- calculations on 10. The Os–P bond distances in 10 [Os(3)–P(2)
tal quality was poor, affording a structure whose convergence 2.3556(18), Os(2)–P(1) 2.3406(17) Å] are comparable to those in
values were >10% and with significant disorder in the phenyl and [Os3(CO)10(l-dppf)] [2.3327(9), 2.3511(9) Å] [52]. The eight
cyclopentadienyl groups. The thermal ellipsoid plot of the crude carbonyls are terminal with two attached to Os(2) and three to
structure confirmed the presence of a triangular array of Os2Sn both Os(1) and Os(3). Cluster 10 is electron-precise based on an
atoms that also contained one bridging dppf and two g1-SnPh3 li- VEC of 48 electrons and each osmium is coordinatively saturated.
gands. Fortunately, the diffraction structure provided sufficient The atomic charges and Wiberg indices for 10 mirror the data
information about the geometry of the cluster core, which in con- computed for the other compounds reported here.
junction with the 1H NMR data that revealed the presence of two The IR spectrum of 10 shows m(CO) absorption bands in the
distinct hydride resonances, facilitated a detailed DFT investigation range 2080–1960 cm1, indicating that all carbonyls are terminal.
on the structural composition of 9. The DFT-optimized structure of Both 1H and 31P{1H} NMR spectra show the existence of two iso-
9-Me is shown in Fig. 3. Each osmium atom contains one r-bonded mers in solution. The 31P{1H} NMR spectrum contains four reso-
SnPh3 ligand and two terminal carbonyls. The computed osmium- nances in two sets of singlets in a 20:1 ratio, at 8.2 and
tin distances are not unlike those distances found in 8 2.7 ppm for the major isomer and 11.5 and 4.9 for the minor
[2.7253(2) Å] [68]. The Ph2Sn and dppf groups serve to tether the component. In accord with this, the hydride region of the 1H
Os1–Os2 vector. Missing from the diffraction structure were the NMR spectrum also contains two sets of resonances in a 20:1 ratio.
two bridging hydrides, which we propose are associated with the The major isomer appears as a doublet at d 19.37 (J = 22.8 Hz) and
Os–Os and Os–(l2)Sn vectors. The 1H NMR data are also in accord two slightly broadened singlets at d 8.66 and 18.64, while the
with the formulated structure (see below). The atomic charge minor isomer is represented by a doublet at d 17.30
326 J.C. Sarker et al. / Inorganica Chimica Acta 409 (2014) 320–329

Table 3
Selected natural charges and Wiberg bond indices for the DFT-optimized structures based on compounds 3, 7, 9-Me, and 10.a

Compound 3 7 9-Me 10
Atomic charge
Os1 1.76 0.66 2.16 1.51
Os2 1.75 0.65 1.91 1.39
Os3 1.82 1.45 1.40
Sn1 1.83 1.78 1.80
Sn2 1.83 1.78
Sn3 1.80
Fe 0.12 0.16 0.15
P1 1.42 1.33 1.38 1.40
P2 1.40 1.33 1.38 1.36
H1 0.12 0.50 0.13 0.09
H2 0.12 0.50 0.01 0.06
H3 0.06
O1 0.80
O2 0.80
Wiberg bond index
Os1–Os2 0.40 0.11 0.22 0.23
Os2–Os3 0.41 0.45 0.23
Os1–Os3 0.42 0.45 0.40
Os1–Sn1 0.55 0.70 0.62
Os2–Sn1 0.25
Os1–Sn2 0.63
Os2–Sn3 0.61
Os1–Sn1 0.55
Os3–Sn1 0.55
Os2–Sn2 0.55
Os3–Sn2 0.55
Os1–P1 0.82 0.68 0.84
Os2–P2 0.82 0.68 0.81
Os2–P1 0.80
Os3–P2 0.76
Os1–O1 0.44
Os2–O1 0.44
Os1–O2 0.44
Os2–O2 0.44
O1–H1 0.73
O2–H2 0.73
Os1–H1 0.71 0.41 0.38
Os2–H1 0.39 0.39
Os2–H2 0.71 0.61 0.37
Os3–H2 0.43
Os2–H3 0.75
Sn1–H2 0.20
Sn3–H2 0.05
a
Atom numbers based on the structures depicted below:
Sn1
Os3 Os3
Sn1 Os1
Sn2 Sn1
H1 H2 H1

O1 Sn3 Sn2
H2 Os2 Os1 H1 Os2 Os1 Os2 Os1 Os3 Os2
O2 H1 H2
H3
P2 P1 P2 H2 P1 P2 P1 P2 P1

Fe Fe Fe

compounds: 3 7 9-Me 10
.

(J = 22.8 Hz) and two multiplets at d 10.22 and 15.91. We 4. Summary and conclusions
suggest that the migration of the hydride ligand between the
Os(1)–Os(2) and Os(1)–Os(3) edges accounts for the observed iso- The 46e diphosphine-bridged dihydride clusters [(l-H)2Os3
mers1 [75]. (CO)8(l-dppm)] (1) and [(l-H)2Os3(CO)8(l-dppf)] (2) are versatile
starting materials for the synthesis new bimetallic osmium-tin
clusters. Cluster 1 containing the rigid dppm ligand reacts with
1
excess Ph3SnH to furnish the distannylene-dihydride cluster
Two possible alternatives for the observed isomerism in the minor species involve
(1) an exchange of the Ph3Sn and CO groups at the Os(1) center and (2) a
[H2Os3(CO)7(l-SnPh2)2(l-dppm)] (3), whose origin results from
conformational change in the ‘‘twist’’ angle of the dppf ligand. the formal elimination of hydrogen and biphenyl. Interestingly,
 J.C. Sarker et al. / Inorganica Chimica Acta 409 (2014) 320–329 327

[H(l-H)2Os3(CO)8(SnPh3)(l-dppm)] akin to cluster 10, and as we

did not observe such a species we speculate that either elimination
of hydrogen or addition of a second equivalent of Ph3SnH to the
putative cluster occurs rapidly under the reaction conditions.
Reaction of cluster 2, containing the highly flexible dppf ligand
[12–18], with Ph3SnH took a quite different course to that seen for
1. Thus, a more complex mixture of products resulted which com-
prised the previously unreported clusters [H(l-H)2Os3(CO)8
(SnPh3)(l-dppf)] (10), [Os3(CO)8(l-OH)2(l-dppf)] (7) and
[(l-H)Os2(CO)4(SnPh3)2(l-HSnPh2)(l-dppf)] (9) together with the
known complexes [Os2(CO)6(SnPh3)2(l-SnPh2)2] (8) and
[HOs(CO)4(SnPh3)] (6). Here it is notable that while tin is incorpo-
rated into the majority of the products, the dppf ligand has been
partially extruded. Cluster 10 is the major isolated species and is
the product of the expected oxidative-addition reaction of the
tin-hydride bond to 2 containing an osmium to tin ratio of 3:1.
The mode of formation of the other products is less clear. Com-
plexes 6 and 9 have osmium to tin ratios of 1:1 and 2:3 respec-
tively and can be envisaged to result from the fragmentation of
an Os3Sn4 cluster, the dppf ligand remaining attached to the dios-
mium complex 9. In support of this speculation we note that 6 and
9 are formed in similar yields. Adams and co-workers have previ-
ously shown that addition of multiple tin-hydride groups to tran-
Fig. 3. The DFT-optimized structure of 9-Me.
sition metal clusters is a relatively common occurrence and in
many cases the nuclearity of the starting transition metal cluster
is not maintained [46–49,68]. Formation of both 7 and 8 was quite
the latter by-product was isolated in similar yields to 3, providing unexpected and consequently are difficult to rationalize. It is
compelling evidence that this is indeed a significant reaction known that metal-bound hydrides can often be converted to hy-
pathway. Two previously prepared triphenyltin clusters droxyl ligands upon chromatography [76]. Cluster 8 (together with
[(l-H)2Os3(CO)8(SnPh3)2(l-dppm)] (4) and [(l-H)2Os3(CO)8 6) has previously been prepared upon addition of excess Ph3SnH to
(SnPh3){l-Ph2PCH2P(Ph)C6H4}] (5) are also products of this reac- [(l-H)Os3(CO)10(SnPh3)] and this pathway conceivably occurs in
tion. In a separate control experiment, cluster 4 was shown to be this case with dppf being eliminated from the triosmium center
unreactive on further heating, showing that it was not an interme- under the forcing conditions.
diate en route to 3. Both 4 and 5 have previously been isolated Yields of all of the products reported in this work are relatively
from the reaction of the lightly-stabilized [(l-H)Os3(CO)8 poor, showing that multiple reaction pathways may be operating;
{l3-Ph2PCH2P(Ph)C6H4}] with Ph3SnH (Scheme 1), [50] which sug- we also note that product characterization is heavily reliant on
gests that under the reaction conditions unsaturated 1 partly con- X-ray crystallography. In order to further support the
verts to the former via hydrogen elimination and the subsequent crystallographic studies, the structures of all new species were
reaction with Ph3SnH accounts for these products. It seems plausi- investigated by DFT calculations, and the computed charges and
ble that the major product 3 is formed via the intermediacy of Wiberg bond indices are consistent with the nature and the bond-

Fig. 4. ORTEP diagram of the molecular structure of [(l-H)2HOs3(CO)8(SnPh3)(l-dppf)] (10) at the 50% probability level (left) the DFT-optimized structure of 10 (right).
328 J.C. Sarker et al. / Inorganica Chimica Acta 409 (2014) 320–329

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