Cleavage of Ge-S and C-H bonds in the reaction of electron-deficient [Os3(CO)8(μ-H)(μ3-Ph2P CH2P(Ph)C6H4)] with Ph3GeSPh: Generation of thiophenol derivatives [Os

Article abstract of DOI:10.1016/j.jorganchem.2008.12.005

Title Full: Cleavage of Ge-S and C-H bonds in the reaction of electron-deficient [Os₃(CO)₈(μ-H)(μ₃-Ph₂P CH₂P(Ph)C₆H₄)] with Ph₃GeSPh: Generation of thiophenol derivati

Full text of DOI:10.1016/j.jorganchem.2008.12.005

Journal of Organometallic Chemistry 694 (2009) 752–756
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Cleavage of Ge–S and C–H bonds in the reaction of electron-deficient
[Os3(CO)8(
thiophenol derivatives [Os3(CO)8(
[Os3(CO)7( -H)( -SPh)( 3-SC6H4)(
l-H)(l3-Ph2PCH2P(Ph)C6H4)] with Ph3GeSPh: Generation of
l
-H)(
-dppm)]
l
-SPh)(
l-dppm)] and
l
l
l
l
b
c
Arun K. Raha a, Shishir Ghosh a, Shariff E. Kabir a, , Brian K. Nicholson , Derek A. Tocher
*
a Department of Chemistry, Jahangirnagar University, Savar, Dhaka-1342, Bangladesh
b Department of Chemistry, University of Waikato, Hamilton, New Zealand
c Department of Chemistry, University College London, 20 Gordon Street, London WC1H OAJ, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 15 October 2008
Received in revised form 30 November 2008
Accepted 1 December 2008
Available online 10 December 2008
Heating the electron-deficient [Os3(CO)8(
80 °C led to the thiolato bridged compounds, [Os3(CO)8(
l
-H)(
l
3-Ph2PCH2P(Ph)C6H4)] (1) and Ph3GeSPh in benzene at
l-H)(l-SPh)(l-dppm)] (2) and [Os3(CO)7(l-
H)( -SPh)( 3-SC6H4)( -dppm)] (3), formed by cleavage of Ge–S and C–S bonds of the ligand, in 40%
l
l
l
and 17% yields, respectively. Both compounds 2 and 3 have been characterized by a combination of ele-
mental analysis, infrared and 1H NMR spectroscopic data together with single crystal X-ray crystallogra-
phy. Compound 3 contains an open triangle of osmium atoms bridged by a SPh and SC6H4 ligands on
opposite sides of the cluster with a dppm ligand bridging one of the Os–Os edges. Compound 2 consists
of a closed triangular cluster of osmium atoms with a bridging SPh, and a bridging hydride ligand on the
same Os–Os edge, and a dppm ligand bridging one of the remaining Os–Os edges.
Keywords:
Triosmium clusters
Bond cleavage (Ge–S, C–H)
Thiophenol
Ó 2008 Elsevier B.V. All rights reserved.
Dppm
X-ray structures
1. Introduction
ported some unusual bimetallic Ru–Sn, Ru–Ge clusters, e.g.
[Ru3(CO)8(l-SPh)2(l3-SnPh2)(SnPh3)2] and [Ru3(CO)8(l-SPh)2(l3-
The electron-deficient triosmium cluster [Os3(CO)8(
l
-H)(l3
-
GePh2)(GePh3)2], from the reactions of Ph3SnSPh or Ph3GeSPh with
Ph2PCH2P(Ph)C6H4)] (1) derived from the decarbonylation of the
[Ru3(CO)12], respectively [18]. We also reported the Os-Sn com-
decacarbonyl compound [Os3(CO)10 -dppm)] has attracted con-
(l
pound [Os3(CO)9(l-SPh)(l3-SnPh2)(NCMe)(g
1-C6H5)2] from the
siderable interest for many years and its chemistry has been thor-
oughly investigated during the last decade to reveal its catalytic
potential as well as applications in organic synthesis [1–15]. With
an electron count of 46, cluster 1 is electron-deficient with respect
to the noble gas rule which requires 48 electrons for a closed trinu-
clear cluster; for this reason it is susceptible to nucleophilic attack
and reacts with a wide range of electron donor ligands under mild
conditions relative to electron precise complexes.
reaction of [Os3(CO)10(NCMe)2] with Ph3SnSPh.
As a part of our studies on bimetallic Os–Ge clusters, we set out
to investigate the reactivity of the electron-deficient 1 with
Ph3GeSPh. Unfortunately, the reaction does not appear to give
any Os–Ge product, instead only the thiolato part of the ligand
incorporated into the cluster resulting in the formation of [Os3(-
CO)8(l-H)(
l-SPh)(l-dppm)] (2) and [Os3(CO)7(l-H)(l-SPh)(l3-
SC6H4)(l-dppm)] (3).
The reactions of 1 with a wide variety of small inorganic and or-
ganic ligands such as CO [4], H2 [5], PR3 [6], P(OR)3 (R = Me, Et, Pri,
Bu, Ph) [6], PPh2H [7], RC„CR (R = Ph, C6H4Me, Me, CF3) [8],
[Au(PPh3)]PF6 [9], EtSH [10], CH3CH(CH3)SH [10], PhSH [10], pySH
[11], HSCH2CH2SH [12], HSCH2CH2CH2SH [12], Se [13], HX (X = Cl,
Br, F, CF3CO2, CH3CO2) [14], CH2N2 [15], silane [16] and Ph3SnH
[17] that afford many interesting and potentially useful com-
pounds have been investigated (Scheme 1). We have recently re-
2. Experimental
All the reactions were performed under a nitrogen atmosphere
using standard Schlenk techniques. Solvents were dried and dis-
tilled prior to use by standard methods. The starting complex
[Os3(CO)8(l-H)(l3-Ph2PCH2P(Ph)C6H4)] (1) and the ligand Ph3GeS-
Ph were prepared according to published procedures [4,19]. Infra-
red spectra were recorded on
a
Shimadzu FTIR 8101
spectrophotometer. 1H NMR spectra were recorded on a Bruker
DPX 400 spectrometer. Elemental analyses were performed by
* Corresponding author. Tel.: +880 406 243 2592; fax: +880 406 243 2477.
E-mail address: skabir_ju@yahoo.com (S.E. Kabir).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.12.005

A.K. Raha et al. / Journal of Organometallic Chemistry 694 (2009) 752–756
753
H
(CO)3
Os
(CO)3
Os
Ph2
P
Ph2
P
Os
(OC)4
Os
(OC)3
Os
P
Os
P
PhS
(CO)3 Ph2
(CO)2 Ph2
110 oC
25 oC 12 h
CO, 2d
- 2CO
Ph
P
Ph
P
CO, 2h
110 oC
Os
(OC)3
Os
Os
(OC)3
Os
(CO)3
(CO)3
H
Os
P
H
Os
P
(CO)2 Ph2
(CO)3 Ph2
1
PR3
CO
Os
R3P
R3P
(CO)3
Os
Ph2
P
80 oC H2
CO
Os
P
(CO)3 Ph2
Ph
+
H
P
(CO)2
Os
Ph2
P
Os
(OC)4
Os
(OC)3
Os
P
(CO)3
Os
(CO)2
P
Ph2
H
R3P
Os
H
(CO)2 Ph2
Scheme 1.
Microanalytical Laboratories, University College London. Fast atom
bombardment mass spectra were obtained on a JEOLSX-102 spec-
trometer using 3-nitrobenzyl alcohol as matrix and CsI as calibrant.
(m, 5H), 6.90 (m, 6H), 6.72 (m, 2H), 2.97 (m, 1H), 1.58 (m, 1H),
À15.66 (t, 1H, J = 7.2 Hz). 31P–{1H} NMR (CDCl3): d 17.2 (d,
J = 94.8 Hz), 21.3 (d, J = 94.8 Hz). FAB mass spectrum: m/z 1370
(M+), 1342 (M+ÀCO), 1314 (M+À2CO), 1286 (M+À3CO), 1258
(M+À4CO), 1230 (M+À5CO), 1202 (M+À6CO), 1174 (M+À7CO).
2.1. Reaction of [Os3(CO)8(l-H)(l3-Ph2PCH2P(Ph)C6H4)] (1) with
Ph3GeSPh
2.2. X-ray crystallography
A benzene (20 mL) solution of 1 (50 mg, 0.042 mmol) and
Ph3GeSPh (35 mg, 0.084 mmol) was heated to reflux for 9 h during
which time the color changed from green to yellow. The progress
of the reaction was followed by spot TLC. The solvent was removed
under reduced pressure and the residue chromatographed by TLC
on silica gel. Elution with hexane/CH2Cl2 (7:3, v/v) developed three
bands. The second band gave the unreacted starting compound 1
Single crystals were mounted on fibres and diffraction data col-
lected at low temperatures (see Table 1) on Bruker AXS SMART
APEX CCD diffractometers using Mo Ka radiation (k = 0.71073 Å).
Data collection, indexing and initial cell refinements were all done
using SMART [20] software. Data reduction was done with SAINT [21]
software and the SADABS program [22] was used to apply empirical
absorption corrections. The structures were solved by direct meth-
ods [23] and refined by full matrix least-squares on F2 [24]. All
non-hydrogen atoms were refined anisotropically and hydrogen
atoms were included using a riding model. For compound 3 the
refinement with just the cluster molecule included converged with
R1 = 0.093. There was considerable diffuse electron density still
remaining (2–3 e AÀ3) and PLATON calculated very large voids in
the lattice. Obviously very poorly ordered solvent, probably CH2Cl2
was present. Since this could not be modeled, it was eliminated
using SQUEEZE procedures [25]. After this treatment refinement
converged to R1 = 0.074. The disordered solvent, combined with a
small poorly diffracting crystal, meant that refinement was less
successful than normal. Only the Os, S, P, and O atoms were refined
anisotropically, since several of the carbon atoms gave positive def-
inite ellipsoids if released from isotropic modeling. The hydride li-
gand could not be located directly but the disposition of the CO
ligands suggest strongly that it bridges the Os(1)–Os(2) edge.
Scattering factors were taken from International Tables for X-ray
(6 mg) while the first and third bands afforded [Os3(CO)8(
-SPh)( -dppm)] (2) (22 mg, 40%) as orange crystals and
[Os3(CO)7( -H)( -SPh)( 3-SC6H4)( -dppm)] (3) (10 mg, 17%) as
l-H)
(l
l
l
l
l
l
pale yellow crystals after recrystallization from hexane/CH2Cl2 at
4 °C. Spectral data for 2: Anal. Calc. for C39H28O8Os3P2S: C, 36.33;
H, 2.19. Found: C, 36.55; H, 2.23%. IR (mCO, CH2Cl2): 2067 vs,
2023 m, 1993 vs, 1970 m, 1955 m, 1923 w cmÀ1. 1H NMR (CDCl3):
d 7.66 (m, 2H), 7.53 (m, 3H), 7.42 (m, 5H), 7.32 (m, 6H), 7.13 (m,
9H), 5.73 (dd, 1H, J = 24.2, 12.5 Hz), 4.56 (dd, 1H, J = 24.2,
12.5 Hz), À15.76 (d, 1H, J = 29.6 Hz). 31P–{1H} NMR (CDCl3): d
À24.1 (br, s), À24.8 (br, s). FAB mass spectrum: m/z 1290 (M+),
1262 (M+ÀCO), 1234 (M+À2CO), 1206 (M+À3CO), 1178
(M+À4CO), 1150 (M+À5CO), 1122 (M+À6CO), 1094 (M+À7CO),
1066 (M+À8CO). Spectral data for 3: Anal. Calc. for
C44H32O7Os3P2S2: C, 38.59; H, 2.36. Found: C, 38.73; H, 2.41%. IR
(
m
CO, CH2Cl2): 2056 s, 2041 vs, 1996 s, 1983 vs, 1953 w, 1940 w
cmÀ1 1H NMR (CDCl3): d 7.83 (dd, 1H, J = 6.8, 3.6 Hz), 7.64 (dd,
1H, J = 6.0, 3.6 Hz), 7.58 (m, 3H), 7.38 (m, 8H), 7.26 (m, 3H), 7.12
.

754
A.K. Raha et al. / Journal of Organometallic Chemistry 694 (2009) 752–756
Table 1
of two triosmium compounds, [Os3(CO)8( -H)(
l
l-SPh)(l-dppm)]
Crystal and structural refinement data for [Os3(CO)8(l-H)(l-SPh)(l-dppm)] (2) and
[Os3(CO)7(
(2) and [Os3(CO)7( -H)( -SPh)( 3-SC6H4)(l-dppm)] (3) in 40%
l
l
l
l
-H)(l
-SPh)(
l
3-SC6H4)(
l
-dppm)] (3).
and 17% yields, respectively (Scheme 2). Compound 2 was previ-
Empirical formula
Formula weight
T (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
C39H28O8Os3P2S
1289.21
150(2)
0.71073
Triclinic
C44H32O7Os3P2S
1368.35
89(2)
0.71073
Monoclinic
P21/n
10.9678(2)
28.0191(2)
18.5013(3)
90
98.894(1)
90
ously reported from the reactions of thiophenol with [Os3(-
CO)9(NCMe)(
and with [Os3(CO)10
l
-dppm)] [27] and 1 [10] at ambient temperature
-dppm)] [28] at 110 °C and was character-
(l
ized spectroscopically. Compounds 2 and 3 do not contain any
Ph3Ge-derived ligand. Compound 2 does not seem to be a precur-
sor of 3 as attempts to obtain 3 by treating 2 with thiophenol in
refluxing benzene for 24 h or in refluxing toluene for 8 h have
failed.
P À1
11.5072(8)
12.3475(8)
15.1330(10)
112.9460(10)
91.0800(10)
106.5390(10)
1877.5(2)
2
b (Å)
c (Å)
a
(°)
The solid-state molecular structure of 2 is shown in Fig. 1, crys-
tallographic data are collected in Table 1, and selected bond
lengths and angles are listed in the caption. The structure is based
upon a triangular arrangement of three osmium atoms coordinated
by eight carbonyl ligands, a bridging bis(diphenylphosphino)meth-
ane (dppm) ligand, a bridging phenylsulfido ligand and a bridging
hydride. The three osmium atoms define an approximate isosceles
triangle of osmium atoms with one long [Os(1)–Os(2) 2.8877(5) Å]
and two comparatively short bonds [Os(1)–Os(3) 2.8549(5) Å and
Os(2)–Os(3) 2.8588(5) Å]. The eight carbonyl ligands are all termi-
nal, three of which are bonded to each of Os(1) and Os(3) while the
other two bond to Os(2). The phenylsulfido ligand spans symmet-
rically across the Os(1)–Os(2) edge [Os(1)–S(1) 2.412(2) Å and
Os(2)–S(1) 2.414(2) Å] with the phenyl ring perpendicularly ori-
ented with respect to the trimetallic plane. The hydride ligand
was located crystallographically but not refined and also spans
the Os(1)–Os(2) edge but lies on the opposite side of the Os3 plane
relative to the phenylsulfido ligand. This observation is consistent
with the lengthening of the Os(1)–Os(2) edge and the opening out
of the carbonyl ligands along this edge [C(1)–Os(1)–Os(2)
116.8(3)°, C(4)–Os(2)–Os(1) 115.1(3)°, and C(5)–Os(2)–Os(1)
b (°)
c
(°)
V (Å3)
5105.07(14)
4
Z
Dcalc (Mg/m3)
2.281
10.320
1200
1.780a
Absorption coefficient (mmÀ1
F(000)
)
7.735a
2564a
Crystal size (mm3)
h range for data collection (°)
Index ranges
0.22 Â 0.16 Â 0.04
0.22 Â 0.10 Â 0.05
1.33–25.72
À12 6 h P 12
À33 6 k P 33
À16 6 l P 22
28287
9664 (0.1269)
99.3
0.7014 and 0.2844
2.77–28.30
À15 6 h P 15
À16 6 k P 16
À20 6 l P 20
16053
8500 (0.0295)
96.7
Reflections collected
Independent reflections
Completeness to h = 67.10°
Maximum and minimum
transmission (Rint
Refinement method (%)
0.6830 and 0.2098
)
Full-matrix least-
squares on F2
8500/0/478
0.933
R1 = 0.0383,
wR2 = 0.1333
R1 = 0.0479,
wR2 = 0.1711
2.3471and À2.284
Full-matrix least-
squares on F2
6267/0/516
Data/restraints/parameters
Goodness-of-fit on F2
1.004
Final R indices [I > 2
r
(I)]
R1 = 0.0743,
wR2 = 0.1528
R1 = 0.1343,
wR2 = 0.1700
2.540 and À2.132
R indices (all data)
Largest difference in peak and
hole (e ÅÀ3
)
a
Not including the disordered solvent that was excluded from the refinement
using the SQUEEZE method (see Ref. [25]).
Crystallography [26]. All pertinent crystal data and other experi-
mental conditions and refinement details are summarized in Table 1.
3. Results and discussion
Reaction of [Os3(CO)8(l-H)(l3-Ph2PCH2P(Ph)C6H4)] (1) with
Ph3GeSPh in refluxing benzene for 9 h resulted in the formation
Ph
P
80 oC
+
Ph3GeSPh
Os
(OC)3
Os
P
(CO)3
Os
H
(CO)2 Ph2
1
S
H
(CO)2 Ph
(CO)3
Os
Ph2
P
2
Os
(OC)3
Os
(OC)3
Os
P
+
Fig. 1. Molecular structure of [Os3(CO)8(l-H)(l-SPh)(l-dppm)] (2) with thermal
ellipsoids drawn at the 50% probability level. Ring hydrogen atoms are omitted for
clarity. Selected bond lengths (Å) and angles (°): Os(2)–Os(3) 2.8588(5), Os(1)–
Os(3) 2.8549(5), Os(1)–Os(2) 2.8877(5), Os(1)–S(1) 2.412(2), Os(2)–S(1) 2.414(2),
Os(2)–P(1) 2.317(2), Os(3)–P(2) 2.333(2), Os(3)–Os(1)–Os(2) 59.709(12), Os(1)–
Os(3)–Os(2) 83.4(3), Os(3)–Os(2)–Os(1) 59.575(12), S(1)–Os(1)–Os(2) 53.28(5),
S(1)–Os(1)–Os(3) 81.16(5), C(1)–Os(1)–Os(2) 116.8(3), C(4)–Os(2)–Os(1) 115.1(3),
C(5)–Os(2)–Os(1) 119.7(3), Os(1)–S(1)–Os(2) 73.50(6), P(1)–C(10)–P(2) 113.6(4).
PhS
Os
P
PhS
Os
P
(CO)2 Ph2
(CO)2
Ph2
H
2
3
Scheme 2.

A.K. Raha et al. / Journal of Organometallic Chemistry 694 (2009) 752–756
755
119.7(3)°]. The dppm ligand bridges the Os(2)–Os(3) edge slightly
asymmetrically [Os(2)–P(1) 2.317(2) Å and Os(3)–P(2) 2.333(2) Å]
and the phosphorus atoms of the ligand occupy equatorial sites
on both osmium atoms as expected. The Os–S and Os–P bond dis-
tances in 2 are similar to those observed in related complexes [10–
12] and the overall structural features are similar to the corre-
similarly spans across the Os(1)–Os(2) bonding edge [Os(1)–S(1)
2.446(4) Å and Os(2)–S(1) 2.404(4) Å]. The hydride ligand was
not located in the structural analysis but clearly bridges the
Os(1)–Os(2) edge, cis to the Os(1)–C(1) and Os(1)–C(3) bonds, from
the lengthening of this edge and widening of the C(1)–Os(1)–Os(2)
and C(3)–Os(2)–Os(1) angles [121.6(5)° and 115.6(5)°]. The dppm
ligand also bridges the same Os–Os edge and the Os–P bond dis-
tances are within the range reported for related compounds
[7,10–12,27,28]. The Os–S bond distances in 3 are also in the range
found in the literature [10–12]. The C–C bond lengths within the
sponding ruthenium compound [Ru3(CO)8(
l
-H)(l-SPh)(l-dppm)]
[29] and the ethanethiol analog [Os3(CO)8(
l
-H)( -SC2H5)(l-
l
dppm)] [10]. The spectroscopic data of 2 are consistent with the so-
lid-state structure and are very similar to those reported previ-
ously [10,28].
phenyl ring of the
l3-SC6H4 ligand do not vary significantly, sug-
The solid-state molecular structure of 3 is depicted in Fig. 2,
crystallographic data are collected in Table 1, and selected bond
lengths and angles are listed in the caption. The molecule consists
of an open triangle of three osmium atoms with two distinctly dif-
ferent metal–metal bonds [Os(1)–Os(2) 2.9817(10) Å and Os(2)–
Os(3) 2.9160(10) Å], seven carbonyl ligands, a bridging phenylsulf-
ido ligand, a bridging dppm ligand, a triply bridging cyclometallat-
ed SC6H4 ligand, and a bridging hydride. The carbonyl ligands are
terminally bonded, two are bonded to each of Os(1) and Os(2)
and the other three to Os(3). An interesting structural feature of
3 is the ortho C–H bond activation of the phenyl ring of one phenyl-
gesting unperturbed benzenoid character in the ring. All other fea-
tures of the molecule are within the expected range and the
molecule is a 50-electron cluster with two formal metal–metal
bonds assuming the phenylsulfido and
l3-SC6H4 ligands serve as
three and four electron donors, respectively.
The spectroscopic data of 3 support the solid-state structure.
The infrared spectrum exhibits absorption bands characteristic
for terminally bonded carbonyl ligands. In addition to the usual
aromatic resonances for the phenyl protons, the 1H NMR spectrum
shows a virtual triplet at d À15.66 (J = 7.2 Hz) for the bridging hy-
dride ligand while the 31P–{1H} NMR spectrum displays two equal
intensity doublets at d 17.2 (J = 94.8 Hz) and 21.3 (J = 94.8 Hz) due
to the phosphorus atoms of the dppm ligand. The FAB mass spec-
trum shows the parent molecular ion peak at m/z 1370 together
with fragmentation peaks due to the sequential loss of all seven
carbonyl groups which are also consistent with the solid-state
structure.
sulfido ligand thus forming a
l3-SC6H4 ligand on the cluster sur-
face, which is spatially oriented such that the plane constituted
by the atoms of this ligand is at 73.6° to the Os3 plane. Surprisingly,
there is only one previous example of a structurally characterized
orthometallated arylthiolate ligand on a cluster, that reported by
Adams et al. [30], in which a
face of a closed Os3 triangle. This is in contrast to the many analo-
gous examples of 3-PC6H3R cyclometallated ligands derived from
phosphines. The covalent Os–C distance in [Os(3)–C(12)
l3-SC6H3Me-p ligand lies across the
In summary, the thiolato compounds [Os3(CO)8( -H)(
l
l-SPh)(l-
l
dppm)] (2) and [Os3(CO)7( -H)( -SPh)( 3-SC6H4)(l-dppm)] (3)
l
l
l
3
have been synthesized and structurally characterized. Compound
3 provides an interesting unique example of multiple additions
of thiolate ligands to a metal carbonyl cluster complex. The forma-
tion of an orthometallated thiolate ligand is also rare.
2.143(17) Å] is quite similar to those observed in related com-
plexes [10,12,27]. The phenylsulfido ligand which lies on the oppo-
site side to the
Os(1)Á Á ÁOs(3) edge [Os(1)–S(2) 2.424(4) Å and Os(3)–S(2)
2.459(5) Å] through the sulfur atom while the 3-SC6H4 ligand
l3-SC6H4 ligand asymmetrically bridges the open
l
Acknowledgement
A.K.R. gratefully acknowledges the University Grants Commis-
sion of Bangladesh for a scholarship and Mr. Rokib Hassan for
arranging XRD data collection for compound 3.
Appendix A. Supplementary material
CCDC 705028 and 704328 contain the supplementary crystallo-
graphic data for 1 and 2. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2008.12.005.
References
[1] J.P. Collman, L.S. Hegedus, J.R. Norton, R.J. Finke, Principles and Applications of
Organotransition Metal Chemistry, University Science Book, Mill Valley, CA,
1987. p. 241.
[2] G. Suss-Fink, F. Neumann, in: F.R. Hartley (Ed.), Chemistry of the Metal–Carbon
Bond, vol. 5, Wiley, New York, 1989. p. 231.
[3] E.L. Muetterties, M.J. Krause, Angew. Chem., Int Ed. Engl. 22 (1983) 35.
[4] J.A. Clucas, D.F. Foster, M.M. Harding, A.K. Smith, J. Chem. Soc., Chem. Commun.
(1984) 949.
[5] J.A. Clucas, M.M. Harding, A.K. Smith, J. Chem. Soc., Chem. Commun. (1985)
1280.
[6] M.P. Brown, P.A. Dolby, M.M. Harding, A.J. Mathews, A.K. Smith, J. Chem. Soc.,
Dalton Trans. (1993) 1671.
[7] K.A. Azam, M.B. Hursthouse, M.R. Islam, S.E. Kabir, K.M.A. Malik, R. Miah, C.
Sudbrake, H. Vahrenkamp, J. Chem. Soc., Dalton Trans. (1998) 1097.
[8] M.P. Brown, P.A. Dolby, M.M. Harding, A.J. Mathews, A.K. Smith, D. Osella, M.
Arbrun, R. Gobetto, P.R. Raithby, P. Zanello, J. Chem. Soc., Dalton Trans. (1993)
827.
Fig. 2. Molecular structure of [Os3(CO)7(l-H)(l-SPh)(l3-SC6H4)(l-dppm)] (3) with
thermal ellipsoids drawn at the 30% probability level. Ring hydrogen atoms are
omitted for clarity. Ring hydrogen atoms are omitted for clarity. Selected bond
lengths (Å) and angles (°): Os(1)–Os(2) 2.9817(10), Os(2)–Os(3) 2.9160(10), Os(1)–
S(2) 2.424(4), Os(1)–S(1) 2.446(4), Os(3)–S(2) 2.459(5), Os(3)–C(12) 2.143(17),
Os(1)–P(1) 2.349(5), Os(2)–P(2) 2.387 (5), Os(3)–Os(2)–Os(1) 83.70(3), S(2)–Os(1)–
Os(2) 82.44(11), S(2)–Os(3)–Os(2) 83.27(10), S(1)–Os(2)–Os(1) 52.71(11), S(1)–
Os(1)–Os(2) 51.44(10), S(2)–Os(1)–S(1) 92.25(15), C(12)–Os(3)–Os(2) 87.6(5),
C(12)–Os(3)–S(2) 91.2(5), C(11)–C(12)–Os(3) 123.0(13), Os(2)–S(1)–Os(1)
75.85(13), Os(1)–S(2)–Os(3) 107.33(17), C(21)–S(2)–Os(1) 109.0(6), C(21)–S(2)–
Os(3) 117.0(6), C(11)–S(1)–Os(1) 116.5(6), C(11)–S(1)–Os(2) 109.5(6), C(1)–Os(1)–
Os(2) 121.6(5), C(3)–Os(2)–Os(1) 115.6(5), P(1)–C(8)–P(2) 112.7(9).

756
A.K. Raha et al. / Journal of Organometallic Chemistry 694 (2009) 752–756
[9] M.M. Harding, B. Kariuki, A.J. Mathews, A.K. Smith, P. Braunstein, J. Chem. Soc.,
Dalton Trans. (1994) 33.
[18] S.E. Kabir, A.K. Raha, M.R. Hassan, B.K. Nicholson, E. Rosenberg, A. Sharmin, L.
Salassa, Dalton Trans. (2008) 4212.
[10] S.M.T. Abedin, K.A. Azam, M.B. Hursthouse, S.E. Kabir, K.M.A. Malik, M.A.
Mottalib, E. Rosenberg, J. Cluster Sci. 12 (2001) 5.
[11] S.E. Kabir, K.M.A. Malik, E. Mollah, M.A. Mottalib, J. Organomet. Chem. 616
(2000) 157.
[12] S.E. Kabir, C.A. Johns, K.M.A. Malik, M.A. Mottalib, J. Rosenberg, Organomet.
Chem. 625 (2001) 112.
[19] C.R. Lucas, Can. J. Chem. 64 (1986) 1758.
[20] SMART Version 5.628, Bruker AXS Inc., Madison, WI, 2003.
[21] SAINT Version 6.36, Bruker AXS Inc., Madison, WI, 2002.
[22] G. Sheldrick, SADABS Version 2.10, University of Göttingen, 2003.
[23] Program XS from SHELXTL package, V. 6.12, Bruker AXS Inc., Madison, WI, 2001.
[24] Program XL from SHELXTL package, V. 6.12, Bruker AXS Inc., Madison, WI, 2001.
[13] S.E. Kabir, S. Pervin, N.C. Sarker, A. Yesmin, A. Sharmin, T.A. Siddiquee, D.T.
Haworth, D.W. Bennett, K.M.A. Malik, J. Organomet. Chem. 681 (2003) 237.
[14] S.E. Kabir, M.A. Miah, N.C. Sarker, G.M.G. Hossain, K.I. Hardcastle, D. Rokhsana,
E. Rosenberg, J. Organomet. Chem. 690 (2005) 3044.
[25] A.L. Spek, PLATON, SQUEEZE, Springer, Berlin, 2003.
[26] A.J.C. Wilson (Ed.), International Tables for X-ray Crystallography, Volume C;
Kynoch, Academic Publishers, Dordrecht, 1992 (Tables 6.1.1.4 (pp. 500–502)
and 4.2.6.8 (pp. 219–222)).
[15] S.M.T. Abedin, K.I. Hardcastle, S.E. Kabir, K.M.A. Malik, M.A. Mottalib, E.
Rosenberg, M.J. Abedin, Organometallics 19 (2000) 5623.
[16] A.J. Deeming Md, M. Hassan, S.E. Kabir, E. Nordlander, D.A. Tocher, J. Chem.
Soc., Dalton Trans. (2004) 3079.
[27] S.R. Hodge, B.F.G. Johnson, J. Lewis, P.R. Raithby, J. Chem. Soc., Dalton Trans.
(1987) 931.
[28] K.A. Azam, S.E. Kabir, A. Miah, M.W. Day, K.I. Hardcastle, E. Rosenberg, A.J.
Deeming, J. Organomet. Chem. 435 (1992) 157.
[17] M.R. Hassan, G. Hogarth, G.M.G. Hossain, S.E. Kabir, A.K. Raha, M.S. Saha, D.A.
Tocher, Organometallics 26 (2007) 6473.
[29] P. Fompeyrine, G. Lavigne, J.J. Bonnet, J. Chem. Soc., Dalton Trans. (1987) 91.
[30] R.D. Adams, J.E. Babin, H.S. Kim, J. Am. Chem. Soc. 109 (1987) 1414.