Synthesis and structure of sulfur and selenium capped dihydride triruthenium clusters [Ru3(CO)7(μ-H)2(μ-dppm)(μ3-E)] (E = S, Se)

Article abstract of DOI:10.1016/j.jorganchem.2008.10.030

Reaction of [Ru₃(CO)₁₀(μ-dppm)] (1) with H₂S at 66 °C affords high yields of the sulfur-capped dihydride [Ru₃(CO)₇(μ-H)₂(μ-dppm)(μ₃-S)] (2), formed by oxidative-addition of both

Full text of DOI:10.1016/j.jorganchem.2008.10.030

Journal of Organometallic Chemistry 694 (2009) 304–308
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Note
Synthesis and structure of sulfur and selenium capped dihydride triruthenium
clusters [Ru3(CO)7( -H)2( -dppm)( 3-E)] (E = S, Se)
l
l
l
Md. Iqbal Hyder a, Noorjahan Begum a, Md. Delwar H. Sikder a, G.M. Golzar Hossain b,
a,
c
Graeme Hogarth c, , Shariff E. Kabir , Christian J. Richard
*
*
a Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh
b Department of Chemistry, University of Dhaka, Dhaka 1000, Bangladesh
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 21 August 2008
Received in revised form 16 October 2008
Accepted 16 October 2008
Available online 25 October 2008
Reaction of [Ru3(CO)10
(
l
-dppm)] (1) with H2S at 66 °C affords high yields of the sulfur-capped dihydride
[Ru3(CO)7(l-H)2(l-dppm)(l3-S)] (2), formed by oxidative-addition of both hydrogen–sulfur bonds.
Hydrogenation of [Ru3(CO)7(
hydrogenation of [Ru3(CO)7(
in 85% yield. The molecular structures of 2 and 5 reveal that the diphosphine and one hydride simulta-
neously bridge the same ruthenium–ruthenium edge with the second hydride spanning one of the non-
bridged edges. Both 2 and 5 are fluxional at room temperature being attributed to hydride migration
l
-dppm)(
l
3-CO)(
l
3-S)] (3) at 110 °C also gives 2 in similar yields, while
3-Se)] (4) affords [Ru3(CO)7( -H)2( -dppm)( 3-Se)] (5)
l
-dppm)(
l
3-CO)(
l
l
l
l
Keywords:
Triuthenium cluster
Dihydride
Sulfide
Selenide
between the non-bridged edges. Addition of HBF4 to 2 affords the cationic trihydride [Ru3(CO)7(
H)3( -dppm)( 3-S)][BF4] (6) in which the hydrides are non-fluxional due to the blocking of the free
ruthenium–ruthenium edge.
l-
l
l
Ó 2008 Elsevier B.V. All rights reserved.
Bridging dppm
Crystal structures
(CO)2
1. Introduction
Os
PPh2
PPh2
(CO)2
Os
S
S
(CO)2
Os
(CO)2Ph2
Os
Ph2P
Ph2P
Transition-metal carbonyl clusters containing triply-bridging
chalcogenide ligands are of interest since they can often be used
to facilitate the synthesis of higher nuclearity clusters [1–4]. In
recent work we have been examining the reactivity of
(OC)
P
3 Os
(CO)2
Me3NO
S
S
S
Os
P
Os
(CO)2
Os
Δ
Ph2
(CO)2
S
Os
(CO)2
[M3(CO)10
(l-dppm)] (M = Os, Ru), [Ru3(CO)12] and [Os3(CO)10
(l3-
CO)( 3-S)(
l
l-dppm)] with a variety of chalcogen-containing ligands
in an effort to develop methods for the systematic synthesis of tri-
metallic clusters containing capping chalcogenide ligands for use
in cluster growth reactions [3–9]. In an earlier paper we reported
In developing our work we sought high yielding routes to the
diphosphine-substituted trinuclear clusters [Ru3(CO)7( -H)2(
dppm)( 3-E)] (E = S, Se) since the presence of the small bite-angle
dppm ligand has been shown to both activate [M3(CO)10 -dppm)]
towards CO loss while also serving to maintain the integrity of
the trinuclear unit [11]. Herein we describe the successful synthesis
of both of these target molecules from reactions of the
l
l-
l
the synthesis of [Os3(CO)7(
[Os3(CO)10 -dppm)] with tetramethylthiourea [8], which we later
successfully converted into hexanuclear [Os6(CO)12 -dppm)2(l3-
l-dppm)(l3-S)2] from the reaction of
(
l
(l
(l
S)2] via a Me3NO-initiated thermal decarbonylation [3]. In related
work, Predieri et al. have reported the preparation of the corre-
dppm-substituted triruthenium clusters [Ru3(CO)10(l-dppm)] and
sponding hexaruthenium cluster, [Ru6(CO)12(l-dppm)2(l3-Se)2],
[Ru3(CO)7( -dppm)( 3-CO)( 3-E)] with the catalytically important
l
l
l
from a similar self-condensation reaction [10].
H2S and H2, respectively.
2. Experimental
All reactions were performed under a nitrogen atmosphere. Re-
agent grade solvents were dried using standard procedures and
were freshly distilled prior to use. Infrared spectra were recorded
* Corresponding authors.
E-mail addresses: g.hogarth@ucl.ac.com (G. Hogarth), 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.2008.10.030

M.I. Hyder et al. / Journal of Organometallic Chemistry 694 (2009) 304–308
305
on a Shimadzu FTIR 8101 spectrometer. 1H and 31P{1H} NMR spec-
Table 1
Crystal data and structure refinement parameters for 2 and 5.
tra were recorded on a Bruker DPX 400 instrument. All chemical
shifts are reported in d units with reference to the residual protons
of the deuterated solvents for proton and to external 85% H3PO4 for
31P chemical shifts. Elemental analyses were performed by the
Microanalytical Laboratories, University College London. Fast atom
bombardment mass spectra were obtained on a JEOL SX-102 spec-
trometer using 3-nitrobenzyl alcohol as matrix and CsI as calibrant.
2
5
Empirical formula
Formula weight
Temperature (K)
Wave length (Å)
Crystal system
Space group
a (Å)
C32H24O7P2Ru3S
917.72
150(2)
C32H24O7P2Ru3Se
964.62
293(2)
0.71073
0.71073
Triclinic
Triclinic
ꢀ
ꢀ
P1
P1
The clusters [Ru3(CO)10
dppm)] [7] and [Ru3(CO)7(
pared according to published procedures.
(
l
-dppm)] [12], [Ru3(CO)7(
l3-CO)(l3-S)(l-
10.5188(3)
11.2719(3)
16.5144(5)
94.344(1)
104.757(2)
112.509(1)
1716.01(8)
2
10.2649(6)
12.4663(7)
14.0895(8)
95.781(1)
90.329(1)
111.099(1)
1671.8(2)
2
l
3-CO)( 3-Se)( -dppm)] [7] were pre-
l
l
b (Å)
c (Å)
a
(°)
b (°)
2.1. Reaction of [Ru3(CO)10(l-dppm)] (1) with H2S
c
(°)
V (Å3)
Z
Hydrogen sulfide was bubbled through a boiling THF solution
(50 mL) of 1 (125 mg, 0.129 mmol) for 1 h. The solvent was re-
moved under reduced pressure and the residue chromatographed
over a column of silica gel. Elution with hexane/CH2Cl2 (2:1, v/v)
gave a single orange band which on removal of solvent afforded
dcalcd. (g cmꢀ3
)
1.776
15.01
900
1.916
25.67
936
Absorption coefficient (cmꢀ1
F(000)
)
Crystal size (mm)
h range for data collection (°)
Limiting indices
0.25 ꢂ 0.15 ꢂ 0.15
2.95–26.04
ꢀ12 6 h 6 12
ꢀ13 6 k 6 13
ꢀ19 6 1 6 20
26723
0.47 ꢂ 0.15 ꢂ 0.12
1.76–28.29
ꢀ13 6 h 6 13
ꢀ15 6 k 6 16
ꢀ18 6 1 6 18
14875
7713 (0.0158)
7713/0/492
1.016
R1 = 0.035,
wR2 = 0.089
R1 = 0.040,
wR2 = 0.092
1.754 /ꢀ1.78
[Ru3(CO)7(
tals from hexane/CH2Cl2 at 20 °C. Anal. Calc. for C32H24O7P2Ru3S:
C, 41.88; H, 2.64. Found: C, 41.98; H, 2.78%. IR (CO) (CH2Cl2):
2062 vs, 2041 vs, 2000 vs, 1993 s, 1943 w, 1869 w cmꢀ1 1H NMR
l-H)2(l-dppm)(l3-S)] (2) (0.092 g, 80%) as orange crys-
t
Reflections collected
.
Independent reflections [R(int)
Data/restraints/parameters
Goodness-of-fit (GOF) on F2
]
6677 (0.0700)
6677/12/436
1.027
(CD2Cl2, 293 K): d 7.54–7.02 (m, 20 H), 3.87 (m, 1H), 3.31 (m, 1H),
ꢀ17.93 (brs, 2H). 1H NMR (CD2Cl2, 213 K): d 7.59–7.04 (m, 20 H),
3.92 (m, 1H), 3.32 (m, 1H), ꢀ17.88 (t, J 6.0, 1H), ꢀ18.06 (d, J 28.0,
1H). 31P{1H} NMR (CD2Cl2, 293 K): d 21.8 (s). 31P{1H} NMR (CD2Cl2,
213K): d 22.3 (d, J 56.7), 20.6 (d, J 56.7). Mass spectrum: m/z 919.
Final R indices [I > 2
r
(I)]
R1 = 0.042,
wR2 = 0.098
R1 = 0.055,
wR2 = 0.103
1.994/ꢀ1.154
R indices (all data)
Largest difference peak/hole
(e Åꢀ3
)
2.2. Hydrogenation of [Ru3(CO)7(l3-CO)(l3-S)(l-dppm)] (3)
Hydrogen was bubbled through a boiling toluene solution
(20 mL) of [Ru3(CO)7( 3-CO)( 3-S)( -dppm)] (3) (85 mg,
0.090 mmol) for 1 h. The solvent was removed under reduced pres-
sure and the residue chromatographed by TLC on silica gel. Elution
with hexane/CH2Cl2 (7:3, v/v) gave an orange band, which afforded
2 (65 mg, 78%).
and initial cell refinements were all done using SMART [13] software.
Data reduction was accomplished with SAINT [14] software and the
SADABS program [15] was used to apply empirical absorption correc-
tions. The structures were solved by direct methods [16] and re-
fined by full matrix least-squares [17]. All non-hydrogen atoms
were refined anisotropically and hydrogen atoms were included
using a riding model. The phenyl rings of the dppm ligand of com-
pound 2 were disordered with the occupancy of 50:50, the carbon–
carbon distance was restrained to 1.39 Å and the 1,3-related dis-
tance to 2.408 Å for the pair of unprimed (C(8) to C(13)) and
primed (C(80) to C(130)) atoms. Additional details of data collection
and structure refinement are given in Table 1.
l
l
l
2.3. Hydrogenation of [Ru3(CO)7(l-dppm)(l3-CO)(l3-Se)] (4)
A similar hydrogenation of 4 (75 mg, 0.076 mmol) for 1 h
followed by chromatographic work-up afforded [Ru3(CO)7-
(l-H)2(l-dppm)(l3-Se)] (5) (62 mg, 85%) as orange crystals after
recrystallization from hexane/CH2Cl2 at 4 °C. Anal. Calc. for
C32H24O7P2Ru3Se: C, 39.84; H, 2.51. Found: C, 40.05; H, 2.71%. IR
3. Results and discussion
t
(CO) (CH2Cl2): 2062 vs, 2041 vs, 2000 vs, 1993 s, 1943 w, 1869
w cmꢀ1 1H NMR (CD2Cl2, 293K): d 7.50–7.18 (m, 20 H), 3.92 (m,
.
1H), 3.27 (m, 1H), ꢀ17.88 (s, 2H). 31P{1H} NMR(CD2Cl2, 213 K): d
24.2 (s). Mass spectrum: m/z 965.
No reaction was observed between [Ru3(CO)10
and H2S at room temperature, however, in boiling thf the sulfur-
capped dihydride [Ru3(CO)7( -H)2( -dppm)( 3-S)] (2) was
(l-dppm)] (1)
l
l
l
isolated in 80% yield after chromatographic separation. The latter
was also obtained in similar yields from the reaction of
2.4. Protonation of 2
[Ru3(CO)7(l-dppm)(l3-CO)(l3-S)] (3) with H2 (1 atm) in toluene
Addition of a drop of HBF4 ꢁ Et2O to an orange CD2Cl2 solution
of 2 led to its rapid decolourisation and clean formation of
at 110 °C. The high temperatures required for this second transfor-
mation are not surprising since the addition of dihydrogen to a sat-
urated 48-electron cluster is expected to have a high activation
energy. Since H2Se is not readily available due to its toxicity, we
[Ru3(CO)7(
l
-H)3(
l
-dppm)(
l
3-S)][BF4] (6). IR
t(CO) (CH2Cl2): 2122
s, 2070 vs, 2021 m cmꢀ1
.
1H NMR (CD2Cl2): d 7.69–7.20 (m, 20
H), 4.14 (m, 1H), 3.68 (m, 1H), ꢀ18.03 (m, 1H), ꢀ18.15 (m, 2H).
utilized the hydrogenation of [Ru3(CO)7(l-dppm)(l3-CO)(l3-Se)]
31P{1H} NMR (CD2Cl2, 213 K): d 29.2 (s).
(4) to give [Ru3(CO)7( -H)2( -dppm)( 3-Se)] (5) in 85% yield
l
l
l
(Scheme 1). Both 2 and 5 were readily characterised on the basis
of analytical and spectroscopic data, while single crystal X-ray dif-
fraction studies were also carried out on both the results of which
are summarized in Figs. 1 and 2 and Table 1.
The two structures are very similar and hence the discussion
will focus on that of 2. The molecule consists of a triangle of ruthe-
nium atoms characterized by three similar but distinct ruthenium-
2.5. X-ray structure determinations
Crystals of 2 and 5 suitable for X-ray analyses were mounted on
fibres and diffraction data collected at low temperature on a Non-
ious Kappa CCD (Bruker AXS) and SMART APEX CCD diffractometer
using Mo K
a radiation (k = 0.71073 Å). Data collection, indexing

306
M.I. Hyder et al. / Journal of Organometallic Chemistry 694 (2009) 304–308
H)2(l3-S)] [2.760(1) Å] [21]. The triply-bridging sulfide ligand caps
the ruthenium triangle in a symmetrical manner, the ruthenium-
sulfur distances [Ru(1)–S(1) 2.365(1), Ru(2)–S(1) 2.367(1), Ru(3)–
S(1) 2.358(1) Å] lying in the range found for [Ru3(CO)9(l-H)2(l3-
S)] [21]. Selenide-capped 5 is very similar. The hydrides were again
crystallographically located on the Ru(2)–Ru(3) and Ru(1)–Ru(2)
edges and the non-hydride bridged Ru(1)–Ru(3) edge is signifi-
cantly shorter than these. The triply-bridging selenide ligand sym-
metrically caps the ruthenium triangle with ruthenium–selenium
distances in the narrow-range of 2.4772(5)–2.4901(5) Å. The over-
all structure of 2 and 5 are very similar to that of the osmium clus-
E
(CO)3
Ru
Ph2
P
(CO)2Ph2
Ru
Ru
(OC)
3 Ru
P
(OC)4
H2S
68 oC
Ru
P
Ru
(CO)2
P
Ph2
H
Ph2
(CO)3
H
1
2, E = S
5, E = Se
H2 110 o
C
ter, [Os3(CO)7(l-H)2(l-dppm)(l3-S)], obtained from the reaction of
[Os3(CO)9( -H)2(
electrons and therefore, each ruthenium atom formally has an
18-electron configuration.
The carbonyl region of the IR spectrum of 2 and 5 are also sim-
ilar to that observed for [Os3(CO)7(l-dppm)(l3-CO)(l3-S)] indicat-
ing that they are also structurally similar in solution. At room
temperature, the 1H NMR spectrum of 2 shows multiplets in the
aromatic region and at d 3.87 and 3.31 assigned to the dppm li-
gand. The hydride region of the spectrum contains a broadened
singlet resonance at d ꢀ17.94 resulting from the rapid exchange
of the hydrides between the non-diphosphine bridged ruthe-
nium-ruthenium edges on the NMR timescale (Scheme 2). The
VT-1H NMR spectra of 2 in the hydride region are depicted in
Fig. 3. The exchange of the hydrides is also apparent in the
l
l
3-S)] with dppm [22]. Both contain 48 valence
E
(CO)2Ph2
Ru
P
P
(OC)3Ru
OC
Ru
Ph2
CO
C
O
3, E = S
4, E = Se
Scheme 1.
Fig. 1. Molecular structure of [Ru3(CO)7(l-H)2(l-dppm)(l3-S)] (2) showing 50%
probability thermal ellipsoids. Hydrogen atoms of the phenyl rings are omitted for
clarity. Selected bond distances (Å) and angles (°): Ru(1)–Ru(2) 2.8723(6), Ru(1)–
Ru(3) 2.7395(6), Ru(2)–Ru(3) 2.9030(5), Ru(1)–S(1) 2.365(1), Ru(3)–S(1) 2.358(1),
Ru(2)–S(1) 2.367(1), Ru(1)–P(1) 2.322(1), Ru(2)–P(2) 2.328(1), Ru(1)–Ru(2)–Ru(3)
56.630(14), Ru(3)–Ru(1)–Ru(2) 62.25(2), Ru(1)–Ru(3)–Ru(2) 61.12(1), Ru(3)–S(1)–
Ru(2) 75.83(4), Ru(3)-S(1)-Ru(1) 70.92(4), Ru(1)–S(1)–Ru(2) 74.75(4), S(1)–Ru(3)–
Ru(1) 54.66(3), S(1)–Ru(2)–Ru(1) 52.59(3), S(1)–Ru(1)–Ru(2) 52.66(3), S(1)–Ru(1)–Ru(3)
54.42(3), S(1)–Ru(3)–Ru(2) 52.23(3), S(1)–Ru(2)–Ru(3) 51.94(3), P(2)–C(20)–P(1)
113.5(2).
Fig. 2. Molecular structure of [Ru3(CO)7(l-H)2(l-dppm)(l3-Se)] (5) showing 50%
probability thermal ellipsoids. Hydrogen atoms of the phenyl rings are omitted for
clarity. Selected bond distances (Å) and angles (°): Ru(1)–Ru(3) 2.7445(4), Ru(1)–
Ru(2) 2.8843(4), Ru(2)–Ru(3) 2.9111(4), Ru(1)–P(1) 2.3165(9), Ru(2)–P(2)
2.3393(9), Ru(1)–Se(1) 2.4772(5), Ru(2)–Se(1) 2.4901(5), Ru(3)–Se(1) 2.4813(5),
Se(1)–Ru(1)–Ru(3) 56.46(1), Se(1)–Ru(1)–Ru(2) 54.71(1), C(11)–Ru(1)–Ru(2)
114.3(1), Ru(1)–Ru(3)–Ru(2) 61.24(1), Ru(1)–Ru(2)–Ru(3) 56.53(1), Ru(1)–Ru(3)–
Ru(2) 61.24(1), C(21)–Ru(2)–Ru(3) 113.4(1), Ru(3)–Ru(1)–Ru(2) 62.23(1), Se(1)–
Ru(2)–Ru(1) 54.30(1), Se(1)–Ru(3)–Ru(1) 56.32(1), Se(1)–Ru(3)–Ru(2) 54.30(1),
P(1)–Ru(1)–Ru(2) 94.28(3), Se(1)–Ru(2)–Ru(3) 54.02(1), P(2)–Ru(2)–Ru(1)
91.85(3), Ru(1)–Ru(2)–Ru(3) 56.53(1), Ru(1)–Se(1)–Ru(3) 67.21(1), Ru(1)–Se(1)–
Ru(2) 70.99(1), Ru(3)–Se(1)–Ru(2) 71.69(2), P(2)–C(90)–P(1) 116.8(2).
ruthenium bond lengths: Ru(1)–Ru(3) 2.7395(6), Ru(1)–Ru(2)
2.8723(6), Ru(2)–Ru(3) 2.9030(5) Å. The diphosphine bridges the
Ru(3)–Ru(2) edge with the phosphorus atoms occupying approxi-
mately equatorial positions and the ruthenium-phosphorus dis-
tances [Ru(1)–P(1) 2.322(1), Ru(2)–P(2) 2.328(1) Å] being
comparable to those in [Ru3(CO)10(l-dppm)] [2.322(2) and
2.334(2) Å] [18]. Both hydrides were crystallographically located
(not refined) across the Ru(1)–Ru(2) and Ru(2)–Ru(3) edges and
their elongation is consistent with hydride bridging [19]. The
non-hydride bridged Ru(1)–Ru(3) edge is significantly shorter than
E
E
(CO)2Ph2
Ru
(CO)2Ph2
Ru
(OC)
P
P
3 Ru
(OC)
3 Ru
the average ruthenium–ruthenium distance in [Ru3(CO)12
[2.854(7) Å] [20] and the unsupported ruthenium-ruthenium
bonds in 1 [2.860(1) and 2.841(1) Å] but comparable to non-hy-
]
Ru
(CO)2
P
Ru
(CO)2
P
H
Ph2
H
Ph2
H
H
dride bridged ruthenium–ruthenium distance in [Ru3(CO)9(
l
-
Scheme 2.

M.I. Hyder et al. / Journal of Organometallic Chemistry 694 (2009) 304–308
307
S
S
BF4
H
(CO)2
Ru
Ph2
P
(CO)2
Ru
Ph2
P
HBF4
(OC)
3 Ru
(OC)
3 Ru
Ru
(CO)2
P
Ru
(CO)2
P
H
Ph2
H
H
Ph2
H
2
6
Scheme 3.
(ꢀ35 °C) the free energy of activation for hydride exchange is esti-
mated as 46 1 kJ molꢀ1. At ꢀ70 °C the hydride region also shows
two signals, a doublet at d ꢀ18.06 (JPH 28.0 Hz) and a triplet at d
ꢀ17.88 (JPH 6.0 Hz). The triplet is assigned to H(2) which bridges
the Ru(2)–Ru(3) edge, and the doublet to H(1) which bridges the
Ru(2)–Ru(1) edge. Data for 5 were similar and will not be discussed
further.
The hydride fluxionality observed for 2 and 5 is possible since
one of the ruthenium-ruthenium edges is always non-bridged. This
edge should be basic enough to bind a proton, which in turn should
block hydride migration. Indeed, addition of HBF4 ꢁ Et2O to a CD2Cl2
solution of 2 resulted in the rapid and quantitative formation of the
trihydride [Ru3(CO)7(l-H)3(l-dppm)(l3-S)][BF4] (6) (Scheme 3).
This was easily shown by 31P NMR spectroscopy, the initial singlet
at 21.8 ppm being replaced by another at 29.2 ppm. Two distinct
hydride signals are now observed in a 2:1 ratio, both appearing
as complex multiplets. Lowering the temperature to ꢀ60 °C had lit-
tle effect on these (or other) signals and we conclude that, as ex-
pected, 6 is non-fluxional.
4. Conclusions
The new clusters [Ru3(CO)7(
[Ru3(CO)7( -H)2( -dppm)( 3-Se)] (5) have been synthesized in
high yields from the reactions of [Ru3(CO)7( -dppm)( 3-CO)(l3
S)] (3) and [Ru3(CO)7( -dppm)( 3-CO)( 3-Se)] (4) with molecular
hydrogen (1 atm). Cluster 2 is also obtained from [Ru3(CO)10
l-H)2(l-dppm)(l3-S)] (2) and
l
l
l
l
l
-
l
l
l
(l-
dppm)] (1) and H2S. The coordination mode adopted by the ligands
in 2 and 5 has been established by NMR spectroscopy and X-ray
crystallography. The hydrogenation of 3 and 4 to give 2 and 5 is
in contrast to that reported for 1 which afforded [Ru3(CO)9(
l-
H)( 3-PhPCH2PPh2)] by loss of a phenyl group by cleavage of a
l
phosphorus-carbon bond [23,24]. Unfortunately, all attempts at
both thermal and Me3NO-initiated decarbonylation reactions of 2
and 5 in efforts to prepare high nuclearity clusters resulted only
in non-specific decomposition.
Supplementary material
CCDC 694984 and 698813 contain the supplementary crystal-
lographic data for 2 and 5. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgments
SEK acknowledges the Royal Society (London) for a fellowship
to work at University College London, and thanks Jahangirnagar
University for sabbatical leave. We thank Professor A.J. Deeming
for collecting the X-ray data for 5.
Fig. 3. The hydride region of the VT-1H NMR spectra of [Ru3(CO)7(
dppm)( 3-S)] (2).
l-H)2(l-
References
l
[1] (a) R.D. Adams, M. Tasi, J. Clust. Sci. 1 (1990) 249;
31P{1H} NMR spectrum which shows a singlet at 21.88 ppm in
CD2Cl2. Upon cooling this signal broadens and at ꢀ60 °C appears
as an AB doublet (JPP 56.7 Hz). From the coalescence temperature
(b) R.D. Adams, I.T. Horvath, L.-W. Yang, J. Am. Chem. Soc. 105 (1983) 1533;
(c) R.D. Adams, I.T. Horvath, J. Am. Chem. Soc. 106 (1984) 1869;
(d) R.D. Adams, I.T. Horvath, H.-S. Kim, Organometallics 6 (1987) 243;
(e) R.D. Adams, Polyhedron 4 (1985) 2003.

308
M.I. Hyder et al. / Journal of Organometallic Chemistry 694 (2009) 304–308
[2] (a) M.L. Steigerwald, Polyhedron 13 (1994) 1245;
[11] G. Hogarth, S.E. Kabir, Coord. Chem. Rev., in press.
(b) T. Shibihara, Coord. Chem. Rev. 123 (1993) 73;
(c) K.H. Whitmire, J. Coord. Chem. 17 (1998) 95;
[12] M.I. Bruce, B.K. Nicholson, M.L. Williams, Inorg. Synth. 26 (1990) 265.
[13] SMART Version 5.628, Bruker AXS, Inc., Madison, WI, 2003.
[14] SAINT Version 6.36, Bruker AXS, Inc., Madison, WI, 2002.
[15] G. Sheldrick, SADABS Version 2.10, University of Göttingen, 2003.
[16] Program XS from SHELXTL package, V. 6.12, Bruker AXS, Inc., Madison, WI, 2001.
[17] Program XL from SHELXTL package, V. 6.12, Bruker AXS, Inc., Madison, WI, 2001.
[18] A.W. Coleman, D.F. Jones, P.H. Dixneuf, C. Brisson, J.J. Bonnet, G. Lavigne, Inorg.
Chem. 23 (1984) 952.
(d) S.W. Audi Fong, T.S.A. Hor, J. Chem. Soc., Dalton Trans. (1999) 639.
[3] T. Akter, N. Begum, D.T. Haworth, D.W. Bennett, S.E. Kabir, Md.A. Miah, N.C.
Sarker, T.A. Siddiquee, E. Rosenberg, J. Organomet. Chem. 689 (2004) 2571.
[4] T. Akter, A.J. Deeming, G.M.G. Hossain, S.E. Kabir, D.N. Mondal, E. Nordlander,
A. Sharmin, D.A. Tocher, J. Organomet. Chem. 690 (2005) 4628.
[5] N. Begum, Md.I. Hyder, M.R. Hassan, S.E. Kabir, D.W. Bennett, D.T. Haworth,
T.A. Siddiquee, D. Rokhsana, A. Sharmin, E. Rosenberg, Organometallics 27
(2008) 1550.
[19] R.G. Teller, R. Bau, Struct. Bond. 41 (1981) 1.
[20] M.R. Churchill, F.J. Hollander, J.P. Hatchinson, Inorg. Chem. 16 (1977) 2655.
[21] T.M. Layer, J. Lewis, A. Martin, P.R. Raithby, W.T. Wong, J. Chem. Soc., Dalton
Trans. (1992) 1411.
[6] S.E. Kabir, M.S. Saha, D.A. Tocher, G.M.G. Hossain, E. Rosenberg, J. Organomet.
Chem. 691 (2006) 97.
[7] S.J. Ahmed, Md.I. Hyder, S.E. Kabir, Md.A. Miah, A.J. Deeming, E. Nordlander, J.
Organomet. Chem. 691 (2004) 309.
[22] 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.
[8] K.A. Azam, G.M.G. Hossain, S.E. Kabir, K.M.A. Malik, Md.A. Mottalib, S. Pervin,
N.C. Sarker, Polyhedron 21 (2002) 381.
[9] S.E. Kabir, S.J. Ahmed, Md.I. Hyder, Md.A. Miah, D.W. Bennett, D.T. Haworth,
T.A. Siddiquee, E. Rosenberg, J. Organomet. Chem. 689 (2004) 3412.
[10] D. Cauzzi, C. Graiff, G. Predieri, A. Tiripicchio, C. Vignali, J. Chem. Soc., Dalton
Trans. (1999) 237.
[23] N. Lugan, J.J. Bonnet, J.A. Ibers, J. Am. Chem. Soc. 107 (1985) 4484.
[24] (a) M.I. Bruce, P.A. Humphrey, B.W. Skelton, A.H. White, M.L. Williams, Aust. J.
Chem. 38 (1985) 1301;
(b) M.I. Bruce, O. Bin Shawkataly, M.L. Williams, J. Organomet. Chem. 287
(1985) 127.