Synthesis of new heterometallic complexes by tin-sulfur bond cleavage of pySSnPh3 (pySH = pyridine-2-thiol) at triruthenium and triosmium centres

Article abstract of DOI:10.1016/j.jorganchem.2010.11.022

The ruthenium-tin complex, [Ru₂(CO)₄(SnPh ₃)₂(μ-pyS)₂] (1), the main product of the oxidative-addition of pySSnPh₃ to Ru₃(CO)₁₂ in refluxing benzene, is [Ru(CO)_2<

Full text of DOI:10.1016/j.jorganchem.2010.11.022

Journal of Organometallic Chemistry 696 (2011) 2153e2160
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis of new heterometallic complexes by tinesulfur bond cleavage
of pySSnPh (pySH ¼ pyridine-2-thiol) at triruthenium and triosmium centres
3
a
a
a
a,
b
*
Arun K. Raha , Shishir Ghosh , Iqbal Hossain , Shariff E. Kabir , Brian K. Nicholson ,
c
d
Graeme Hogarth , Luca Salassa
Department of Chemistry, Jahangirnagar University, Savar, Dhaka-1342, Bangladesh
Department of Chemistry, University of Waikato, Hamilton, New Zealand
Department of Chemistry, University College London, 20 Gordon Street, London WC1H OAJ, UK
Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, UK
a
b
c
d
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 9 October 2010
Received in revised form
3 2 2
The rutheniumetin complex, [Ru (CO) (SnPh ) (m-pyS) ] (1), the main product of the oxidative-addition
2
4
of pySSnPh
give [Ru(CO)
butterfly clusters [MRu
Os (CO)10(NCMe)
with unsaturated [Os
-dppm)] (6) and the new bimetallic cluster [Os
3
to Ru
3
(CO)12 in refluxing benzene, is [Ru(CO)
2
(pyS)(SnPh
(CO)12 or [Os
-pyS)] (3, M¼Ru; 4, M¼Os). Direct addition of pySSnPh
(CO) (SnPh )( -pyS)] (5) as the only bimetallic compound, while
CH P(Ph)C }( -H)] the previously reported [Os (CO) -pyS)( -H)
(CO) (SnPh ){ -Ph PCH P(Ph)C }( -pyS)[( -H)] (7)
3
)] synthon. It reacts with PPh
(CO)10(NCMe) ] to afford the
to
3
to
2
2
(SnPh
3
)(PPh
3
)(
k
-pyS)] (2) and further with Ru
3
3
2
13 November 2010
3
(CO)12(SnPh
3
)(
m
3
3
Accepted 15 November 2010
ꢀ
[
3
2
] at 70 C gives [Os
3
9
3 3
m
3
(CO)
8
{m
3
-PPh
2
2
6
H
4
m
3
8
(
m
m
Keywords:
(
m
3
7
3
m
2
2
6
H
4
m
m
pySSnPh
3
ꢀ
are formed at 110 C. Compounds 1, 2, 4, 5 and 7 have been characterized by X-ray diffraction studies.
Ó 2010 Elsevier B.V. All rights reserved.
Tinesulfur bond cleavage
Butterfly clusters
Mixed-metal cluster
X-ray structure
1
. Introduction
sulfur atoms into transition metal clusters [30], reaction of Ru
with Ph Sn-SPh affording bimetallic [Ru (CO) (SnPh -SnPh
-SPh) ] resulting from both tinesulfur and tinecarbon bond
3
(CO)12
3
3
8
3 2 3
) (m
2
)
Transition metaletin complexes have attracted considerable
interest primarily because tin can be used to modify bimetallic
catalysts, improving their reactivity and product selectivity in
a variety of chemical transformations [1e13]. Further it has recently
been found that the binding of metallic nanoparticles to oxide
supports can be enhanced by the incorporation of tin [10e14]. There
are several methods for the incorporation of tin into transition metal
complexes. The most widely used method is the oxidative-addition
of organotin hydrides and using this methodology a number of
transition metaletin clusters with intriguing structural features have
been synthesized, as exemplified by the work of Adams and
coworkers [15e26]. More recently other tin-element oxidative-
addition reactions have been exploited, for example Gárate-Morales
and Fernández-G have prepared amine-containing osmiumetin
compounds via the cleavage of the nitrogenetin bond in amino-
stannanes [27e29]. Our group have shown that tetraphenylth-
iostannane is an excellent source for the inclusion of both tin and
(m
2
cleavage (Scheme 1) [30,31].
If tin-containing transition metal clusters are to be used towards
the synthesis of catalytically active nanoparticles then facile and
high-yielding routes to these clusters is a necessity [32]. We were
encouraged by the facile nature of the tinesulfur bond cleavage
(Scheme 1) but sought to limit this to a single addition rather than
the multiple addition products found with Ph Sn-SPh. In order to
3
do this we considered the introduction of a thiolate ligand with
secondary binding sites and consequently we have investigated
3
reactions of pyridine-2-thiolate-triphenyltin (pySSnPh ) with
triruthenium and triosmium clusters. Thus, in contrast to the
phenylsulfide ligand which generally acts either as a terminal
PhS
(CO)
Ru
2
SPh
Ru
3
(CO)12
0 o
Ph Sn
3
SnPh
3
Ru
Ru
Ph
SnPh3
8
C
(CO)
3
(CO)
S
3
Sn
Ph
2
*
Corresponding author. Tel.: þ406 243 2592; fax: þ406 243 2477.
E-mail address: skabir_ju@yahoo.com (S.E. Kabir).
Scheme 1.
0
022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.11.022

2154
A.K. Raha et al. / Journal of Organometallic Chemistry 696 (2011) 2153e2160
þ
þ
þ
MS: m/z 1200 (M ), 1172 (M ꢁ CO) , 1144 (M ꢁ 2CO) , 1088
þ
þ
þ
þ
(
M ꢁ 4CO) , 976 (Mꢁ8CO) , 920 (M ꢁ 10CO) , 864 (M ꢁ 12CO) .
S
N
S
N
S
N
2
.2. Reaction of 1 with PPh
3
M
M
M
M
A benzene solution (20 mL) of 1 (30 mg, 0.024 mmol) and tri-
phenylphosphine (13 mg, 0.049 mmol) was stirred at room
temperature for 48 h during which time the color of the reaction
mixture changed from yellow to colorless. The solvent was
removed under reduced pressure and the residue separated by TLC
S
N
S
N
S
N
2 2
on silica gel. Elution with hexane/CH Cl (1:1, v/v) developed one
M
M
M
M
M
M
M
major and several minor bands. The major band afforded [Ru
2
(CO)
2
(SnPh
3
)(PPh
3
)(k
-pyS)] (2) (37 mg, 87%) as colorless crystals
Chart 1.
ꢀ
after recrystallization from hexane/CH
2
Cl
2
at 4 C while the
contents of the minor bands were too small for characterization.
Spectral data for 2: Anal. Calcd for C43 PRuSSn: C, 58.72; H,
3.90; N, 1.59. Found: C, 59.43; H, 3.99; N, 1.65%. IR ( CO, CH Cl ):
7.50(m, 6H) 7.35 (m, 9H),
one-electron, or bridging three-electron, donor ligand, the pyri-
dine-2-thiolate ligand (pyS) can coordinate to metal centres in
a wide variety of ways (Chart 1) which in turn is expected to
influence the nature of the products formed. Indeed this is the case
as we have found that the presence of the coordinating nitrogen
atom substantially affects the course of the reactions and we
obtained a completely different set of products to the related
H34NO
2
n
2
2
ꢁ1 1
3
2014 vs, 1957 vs cm . H NMR (CDCl ): d
7.27 (m, 6H), 7.17 (m, 10H), 6.54 (t, J ¼ 7.6 Hz, 1H), 6.08 (t, J ¼ 7.6 Hz,
31
1
1H), 5.73 (d, J ¼ 7.6 Hz, 1H); P{ H} NMR (CDCl
3
): d 29.8 (s). MS
þ
(FAB): m/z 879 (M ).
reactions with PhS-SnPh
. Experimental section
All the reactions were carried out under a nitrogen atmosphere
3
. These findings are presented herein.
3 2
2.3. Reaction of 1 with [Os (CO)10(NCMe) ]
A benzene solution (30 mL) of [Os
.110 mmol) and 1 (68 mg, 0.055 mmol) was heated at 70e75 C for
3
(CO)10(NCMe)
2
] (103 mg,
2
ꢀ
0
1
.5 h. The solvent was removed in vacuo and the residue chromato-
graphed by TLC on silica gel. Elution with hexane/CH Cl (7:3, v/v)
developed one major and several minor bands. The major band
2
2
using standard Schlenk techniques. Reagent-grade solvents were
dried using appropriate drying agents and were freshly distilled
afforded [RuOs
crystals after recrystallization from hexane/CH
3
(CO)12(SnPh
3
)(
m
3
-pyS)] (4) (64 mg, 40%) as red
prior to use by standard methods. Os
purchased from Strem Chemicals Inc. and used without further
purification, [Os (CO)10(NCMe) ] [33], [Os (CO) -PPh CH P(Ph)
}( -H)] [34] and pySSnPh [31,35,36] were prepared according
to the literature procedures. Pyridine-2-thiol, Ph SnCl and PPh
were purchased from Aldrich and used as received. Infrared spectra
3 3
(CO)12 and Ru (CO)12 were
ꢀ
Cl
2 2
at 4 C while the
contents of the minor bands were too small for characterization.
Spectral data for 4: Anal. Calcd for C35 RuSSn: C, 28.63; H,
.30; N, 0.95. Found: C, 28.86, H,1.35; N, 0.98%. IR ( CO, CH Cl ): 2105
m, 2040 s, 2023 m, 1998 w, 1977 w, 1963 w cm . H NMR (CDCl ):
8.76 (d, J ¼ 6.0 Hz,1H), 8.03 (d, J ¼ 6.0 Hz,1H), 7.59 (m, 7H), 7.31 (m,
3
2
3
8
{m
3
2
2
H19NO12Os
3
C
H
6 4
m
3
1
n
2
2
3
3
ꢁ1 1
3
d
1
were recorded on a Shimadzu FTIR 8101 spectrophotometer.
NMR spectra were recorded on a Bruker DPX 400 instrument. All
chemical shifts are reported in units with reference to the residual
H
þ
þ
9
1
H), 6.63 (t, J ¼ 6.0 Hz,1H). FAB MS: m/z 1469 [M] ,1413 (M ꢁ 2CO) ,
þ
þ
301 (M ꢁ 6CO) , 1189 (M ꢁ 10CO) . ESI-MS (in MeOH with added
d
ꢁ
ꢁ
NaOMe [37]): m/z 1500 (M þ OMe) , 1472 (M ꢁ CO þ OMe) .
protons of the deuterated solvents. Fast atom bombardment mass
spectra were obtained on a JEOLSX-102 spectrometer using
2
.4. Reaction of [Os
3
(CO)10(NCMe)
2
] with pySSnPh
3
3
-nitrobenzyl alcohol as matrix and CsI as calibrant.
3 2
A benzene solution (30 mL) of [Os (CO)10(NCMe) ] (103 mg,
2
.1. Reaction of Ru
3
(CO)12 with pySSnPh
3
0.110 mmol) and pySSnPh (78 mg, 0.169 mmol) was heated to
3
reflux for 3.5 h during which time the color of the reaction mixture
changed from yellow to orange. The solvent was removed under
reduced pressure and the residue separated by TLC on silica gel.
To
a
benzene solution (30 mL) of Ru
3
(CO)12 (100 mg,
0
.156 mmol) was added pySSnPh
3
(147 mg, 0.319 mmol) and the
reaction mixture was heated to reflux for 45 min. The solvent was
removed in vacuo and the residue chromatographed by TLC on silica
Elution with hexane/CH
several minor bands. The major band afforded [Os
3
(m -pyS)] (5) (58 mg, 41%) as orange crystals after recrystallization
2
Cl
2
(7:3, v/v) developed one major and
3
(CO) (SnPh )
9
3
gel. Elution with hexane/CH
The first band gave unconsumed starting material (25 mg) while
the second and third band afforded [Ru (CO)12(SnPh )( -pyS)] (3)
(CO) (SnPh -pyS) ] (1)
2
Cl
2
(4:1, v/v) developed three bands.
ꢀ
2 4 2
H Cl at 4 C. Spectral data for 5: Anal. Calcd for
from hexane/C
Os SSn: C, 29.96; H, 1.49; N, 1.09. Found: C, 30.37; H,
1.56; N, 1.14%. IR ( CO, CH Cl ): 2080 s, 2038 vs, 2021 s, 2000 s,
1975 m cm . H NMR (CDCl ):
4
3
m
C
32
H19NO
9
3
(
19 mg, 10%) as violet crystals and [Ru
2
4
3
)
2
(m
2
n
2
2
ꢁ
1 1
(
CH
u
83 mg, 43%) as yellow crystals after recrystallization from hexane/
3
d
9.05 (d, J ¼ 7.6 Hz, 1H), 7.54 (m,
ꢀ
2
Cl
Sn
2
at 4 C. Spectral data for 1: Anal. Calcd for C50
H
38
N
2
O
4
R-
6H), 7.42 (t, J ¼ 7.6 Hz, 1H), 7.31 (m, 9H), 7.05 (t, J ¼ 7.6 Hz, 1H), 6.85
þ
2
S
2
2
: C, 48.64; H, 3.10; N, 2.27. Found: C, 49.02; H, 3.17; N, 2.31.
(d, J ¼ 7.6 Hz, 1H). MS (FAB): m/z 1283 (M ).
þ
MS (FAB): m/z 1234 (M ). IR (
n
CO, CH
7.38 (m, 14H), 7.18 (m, 18H), 6.85 (t,
J ¼ 6.4 Hz, 2H), 6.48 (t, J ¼ 6.4 Hz, 2H), 6.02 (d, J ¼ 6.4 Hz, 2H). FAB
2 2
Cl ): 2029 s, 2016 s, 1968 s,
ꢁ
1 1
1
956 s cm . H NMR (CDCl
3
):
d
3 8 3 2 2 6 4
2.5. Reaction of [Os (CO) {m -PPh CH P(Ph)C H }(m-H)] with
pySSnPh
3
þ
þ
þ
MS: m/z 1234 (M ), 1206 (MꢁCO) , 1178 (Mꢁ2CO) , 1150
þ
þ
(
C
1
1
M ꢁ 3CO) , 1122 (M ꢁ 4CO) . Spectral data for 3: Anal. Calcd for
SSn: C, 35.01; H, 1.60; N, 1.17. Found: C, 35.43, H,
.66; N, 1.20. IR ( CO, CH Cl ): 2098 m, 2039 s, 2021 m, 1997 w,
968 w cm . H NMR (CDCl ):
8.58 (d, J ¼ 6.0 Hz, 1H), 8.20 (d,
J ¼ 6.0 Hz, 1H), 7.57 (m, 7H), 7.31 (m, 9H), 6.68 (t, J ¼ 6.0 Hz,1H). FAB
3 8 3 2 2 6 4
A toluene solution (20 mL) of [Os (CO) {m -PPh CH P(Ph)C H }
35
H
19NO12Ru
4
(m
-H)] (50 mg, 0.042 mmol) and pySSnPh
3
(40 mg, 0.087 mmol) was
n
2
2
heated to reflux for 2.5 h during which time the color of the reaction
mixture changed from green to yellow. The solvent was removed
under reduced pressure and the residue separated by TLC on silica gel.
ꢁ
1 1
3
d

A.K. Raha et al. / Journal of Organometallic Chemistry 696 (2011) 2153e2160
2155
Elution with hexane/CH
band was unreacted starting cluster (5 mg) while the second and
third bands afforded [Os (CO) (SnPh ){ -Ph PCH P(Ph)C }( -pyS)
-H)] (7) (26 mg, 38%) as yellow crystals and [Os (CO) -pyS)( -H)
2
Cl
2
(1:1, v/v) developed five bands. The first
positions. Crystallographic details are given in Table 1. The deter-
minations were straightforward, except for that of 4. For this
compound the crystal did not diffract well, so the dataset was
3
7
3
m
2
2
6 4
H m
[(m
3
8
(m
m
weaker than optimal (I/s(I) 3.9). The Sn atoms were equally disor-
(
m
-dppm)] (6) (16 mg, 29%) as yellow crystals after recrystallization
dered over two sites and this was included in the refinement. The
phenyl rings were therefore also disordered but could not be
separated into two components so were included as rigid hexagons
with isotropic temperature factors. The final difference map
showed several large peaks located adjacent to CO ligands which
indicated some disorder with these which could not be included
sensibly. Hence the determination was less than ideal but overall
features are unambiguous.
ꢀ
from hexane/CH
2 2
Cl
at 4 C. The other two bands were too small for
complete characterization. Spectral data for 6: Anal. Calcd for
Os S: C, 35.37; H, 2.11; N, 1.09. Found: C, 35.64; H, 2.18;
N, 1.15%. IR ( CO, CH Cl ): 2049 vs, 2014 s, 1989 vs, 1973 sh, 1946 m,
922 w cm . H NMR (CDCl ):
8.45 (d, J ¼ 4.6 Hz, 1H), 7.64 (m, 2H),
.51 (m, 5H), 7.44 (m, 4H), 7.28 (m, 5H), 7.19 (m, 5H), 6.98 (m, 2H), 5.53
C
38
H27NO
8
3 2
P
n
2
2
ꢁ
1 1
1
7
(
(
(
3
d
31
1
m, 1H), 4.79 (m, 1H), ꢁ15.90 (d, J ¼ 30.8 Hz, 1H); P{ H} NMR
CDCl
3
):
d
ꢁ23.4 (d, J ¼ 41.8 Hz, 1P), ꢁ24.5 (d, J ¼ 41.8 Hz, 1P). MS
þ
FAB): m/z 1291 (M ). Spectral data for 7: Anal. Calcd for
2.7. Computational details
C
55
H
41NO
7
Os
3
P
2
SSn: C, 41.00; H, 2.56; N, 0.87. Found: C, 41.53; H,
CO, CH Cl ): 2069 s, 2022 m,1994 vs,1953 m,1933
): 7.84 (m, 6H), 7.67 (m, 2H), 7.59 (m, 1H),
.48 (m, 3H), 7.31 (m, 6H), 7.16 (m, 11H), 7.08 (m, 2H), 6.97 (m, 2H),
2
.62; N, 0.91%. IR (
n
2
2
Calculations were performed on all derivatives with the
Gaussian 03 (G03) program package [42] employing the DFT
method with Becke three parameter hybrid functional [43] and
LeeeYangeParr’s gradient corrected correlation functional [44]
(B3LYP). The LanL2DZ basis set [45] and effective core potential
were used for the Os atoms and the split-valence 6e31G** basis set
ꢁ
1 1
m cm . H NMR (CDCl
7
3
d
6
.76 (m, 2H), 6.65 (m, 1H), 6.18 (m, 2H), 4.96 (m, 1H) 3.86 (m, 1H),
31
1
ꢁ
16.62 (dd, J ¼ 16.4, 2.8 Hz, 1H); P{ H} NMR (CDCl
3
):
d
ꢁ5.5 (d,
þ
J ¼ 54.1 Hz, 1P), ꢁ28.5 (d, J ¼ 54.1 Hz, 1P). MS (FAB): m/z 1611 (M ).
[46] was applied for all other atoms. The geometry of the clusters,
2
.6. X-ray crystallography
as well as the electronic structures, was calculated in the gas phase.
The natural bonding orbital (NBO) method of Weinhold and
coworkers [47] was employed for the electronic structure analysis
of all compounds.
Single crystals of 1, 2, 4, 5 and 7 suitable for X-ray diffraction
were grown by slow diffusion of hexane into a dichloromethane
solution at 4 C. All geometric and crystallographic data were
ꢀ
collected at low temperatures (see Table 1) on a Bruker SMART
3. Results and discussion
APEX CCD diffractometer using Mo-K
Data reduction and integration were carried out with SAINT and
absorption corrections were applied using the program SADABS
a
radiation (
l
¼ 0.71073 Ǻ).
3.1. Reaction of Ru
[Ru (CO) (Ph Sn)
3
(CO)12 with pySSnPh
3
: synthesis of
2
4
3
2
(
m
-pyS) ] (1)
2
[
38]. Structures were solved by direct methods and developed and
2
refined on F using the SHELXL programmes [39] operating under
Treatment of Ru
gives as the major reaction product the Ru
3
(CO)12 with pySSnPh
3
in refluxing benzene
Sn complex
WinGX [40,41]. Hydrogen atoms were included in calculated
2
2
Table 1
Crystallographic data and structure refinement for 1, 2, 4, 5 and 7.
Compound
1
2
4
5
7
Empirical formula
Formula weight
Temp (K)
C
50
H
38
N
2
O
4
2
Ru S
2
Sn
2
C
43
H
34NO
2
PRuSSn
C
35
H
19NO12Os
3
RuSSn
C
32
H
19NO
9
Os
3
SSn
C
55 7 3 2
H41NO Os P SSn
1234.46
89(2)
0.71073
Monoclinic
P2 /c
10.2388(2)
16.1000(4)
28.0081(6)
90
95.009(1)
90
4599.4(2)
4
1.783
1.855
879.50
150(2)
0.71073
Monoclinic
P2 /c
15.059(2)
12.584(2)
20.157(3)
90
102.463(3)
90
1467.93
89(2)
0.71073
Triclinic
P-1
12.9069(4)
16.3814(5)
19.3551(7)
103.160(2)
106.853(2)
90.097(2)
3803.6(2)
4
1282.83
89(2)
0.71073
Triclinic
P-1
1611.18
150(2)
0.71073
Monoclinic
P2 /c
15.886(1)
25.629(2)
12.457(11)
90
93.902(1)
90
5059.9(7)
4
2.115
8.156
ꢀ
Wavelength (A)
Crystal system
Space group
1
1
1
ꢀ
a/A
8.2429(2)
ꢀ
b/A
11.6025(3)
18.4101(4)
71.908(1)
82.836(1)
82.025(1)
1651.23(7)
2
ꢀ
c/A
ꢀ
ꢀ
a
/
b
/
ꢀ
g
/
ꢀ
3
V/A
3729.7(10)
4
1.566
Z
D
m
calc (Mg m 3
ꢁ
)
2.563
11.137
2.580
12.371
(Mo K
a
) (mmꢁ1)
1.211
F(000)
2416
1760
2680
1168
3032
Crystal size (mm)
0.30 ꢂ 0.28 ꢂ 0.16
0.16 ꢂ 0.08 ꢂ 0.07
2.73e28.30
ꢁ19 ꢃ h ꢃ 19
ꢁ16 ꢃ k ꢃ 16
ꢁ26 ꢃ l ꢃ 26
31177
0.22 ꢂ 0.22 ꢂ 0.10
0.28 ꢂ 0.20 ꢂ 0.14
1.86e26.40
ꢁ10 ꢃ h ꢃ 10
ꢁ14 ꢃ k ꢃ 14
ꢁ23 ꢃ l ꢃ 22
16161
0.16 ꢂ 0.14 ꢂ 0.07
2.67e28.30
ꢁ21 ꢃ h ꢃ 21
ꢁ34 ꢃ k ꢃ 33
ꢁ16 ꢃ l ꢃ 16
42847
ꢀ
q
range ( )
1.46e26.39
1.45e27.95
Index ranges
ꢁ12 ꢃ h ꢃ 12
ꢁ17 ꢃ h ꢃ 17
ꢁ21 ꢃ h ꢃ 21
ꢁ25 ꢃ h ꢃ 25
86066
ꢁ
12 ꢃ k ꢃ 20
35 ꢃ l ꢃ 29
ꢁ
Reflections collected
27069
Independent reflections (Rint
Max. and min. transmission
Data/restraints/parameters
Goodness-of-fit on F2
)
9393 (0.0186)
0.7556 and 0.6060
9393/0/559
1.094
8897(0.0350)
0.9200 and 0.8298
8897/0/451
1.024
17992(0.0956)
0.4022 and 0.1931
17992/48/739
1.094
6727(0.0213)
0.198 and 0.127
6727/0/424
1.022
12112(0.0441)
0.5991 and 0.3553
12112/0/631
1.014
Final R indices [I > 2
s
(I)]
R
1
¼ 0.0210,
wR
¼ 0.451
¼ 0.0256,
wR
¼ 0.469
0.61 and ꢁ0.61
R
1
¼ 0.0332,
wR
¼ 0.0764
¼ 0.0441,
wR
¼ 0.0802
1.32 and ꢁ0.44
R
1
¼ 0.0653
wR
¼ 0.1542
¼ 0.1588
wR
¼ 0.2213
5.91 and ꢁ2.70
R
1
¼ 0.0211,
wR
¼ 0.0466
¼ 0.0233,
wR
¼ 0.0476
1.13 and ꢁ1.23
R
1
¼ 0.0310,
wR
¼ 0.0663
¼ 0.0399,
wR
¼ 0.0691
1.54 and ꢁ0.94
2
2
2
2
2
R indices (all data)
R
1
R
1
R
1
R
1
R
1
2
2
2
2
2
ꢀ
ꢁ3
Largest difference in peak and hole (e A
)

2156
A.K. Raha et al. / Journal of Organometallic Chemistry 696 (2011) 2153e2160
N
N
N
N
Ru
3
(CO)12
OC
Ph Sn
S
SnPh3
CO
OC
S
SnPh3
CO
Ru
Ru
CO
SnPh
3
80 o
Ru
OC
Ru
CO
3
S
N
S
C
Ph Sn
3
S
OC
1
25 o
C
1
Os
3
(CO)10(MeCN)
2
PPh
3
Scheme 2.
Ru
(CO)12
0-65 o
3
N
6
C
S
N
[
Ru
2
(CO)
4
(Ph
3
Sn)
2
(
m
-pyS)
2
] (1), isolated as a yellow air-stable
Ph
3
Sn
OC
Ru
PPh
3
S
OC
Ph Sn
crystalline product in 43% yield (Scheme 2). A minor product (10%)
of the reaction is [Ru (CO)12(SnPh )( -pyS)] (3) discussed below.
Ru
OC
Os(CO)3
Os(CO)
4
3
CO
4
3
m
Os
(
CO)
3
N
2
The solid-state molecular structure of 1 is shown in Fig. 1 and
selected bond distances and angles are listed in the caption. Each
ruthenium is also bonded to two carbonyls which are mutually
cis and a triphenyltin ligand, the latter occupying an equatorial
coordination site. Two pyridine-2-thiolate ligands bridge the dir-
OC
Ph Sn
S
Ru
OC
4
Ru(CO)
Ru(CO)
3
3
Ru
4
(
CO)
3
3
uthenium centre to create a non-planar Ru
S
2 2
ring with a dihedral
ligands,
Scheme 3.
ꢀ
angle of 18.9 between the RuS
2
planes and the two SnPh
3
butterfly clusters [50e52]. Given the close structural resemblance
of 1 to these complexes we thus considered using the latter as
a source of the 16-electron fragment, Ru(CO)
this is the case. Treatment of 1 with two equivalents of PPh
room temperature resulted in the clean formation of mononuclear
the latter lying approximately trans to one another (anti). The ruth-
ꢀ
eniumeruthenium distance of 3.64 A is clearly non-bonding and
2
(pyS)(SnPPh
3
). Indeed
each ruthenium atom achieves an 18-electron configuration without
such an interaction but considering the pyridine-2-thiolate ligand
serves as a five-electron donor. The molecule adopts a chiral struc-
3
at
2
[
(
d
Ru(CO)
Scheme 3). The P{ H} NMR spectrum displays only a singlet at
32.8 whereas the FAB mass spectrum shows the parent molecular
2 3 3
(SnPh )(PPh )(k -pyS)] (2) in essentially quantitative yield
ture with C
(CO) -pyS)
ligand on each metal in these complexes is replaced by the terminal
SnPh ligands in 1. The RueSn and RueN bond distances in 1 [Ru(1)e
Sn(1) 2.6457(2) A and Ru(2)eSn(2) 2.6576(2) A; Ru(1)eN(1) 2.1030
2
symmetry and the overall structure is very similar to
31
1
[M
2
6
(m
2
] (M ¼ Mn, Re) except that one equatorial carbonyl
ion at m/z 879. We also determined the single-crystal structure of 2
which is depicted in Fig. 2 with the caption containing selected
3
ꢀ
ꢀ
ꢀ
ꢀ
(
19) A and Ru(2)eN(2) 2.1259(19) A] are similar to those found in
the literature [20,21,30,48,49], while the RueS bond distances
ꢀ
ꢀ
[
(
Ru(1)eS(1) 2.4947(6) A, Ru(1)eS(2) 2.5241(6) A, Ru(2)eS(1) 2.5214
ꢀ
ꢀ
6) A and Ru(2)eS(2) 2.4790(6) A] are significantly longer than those
normally observed in related complexes [48,49]. Spectroscopic
data are fully consistent with the solid-state structure. Notably
a single isomer is seen suggesting that the syn isomer is sterically
disfavored.
2 3
3.2. Cluster 1 as an Ru(CO) (pyS)(SnPh ) synthon
In recent work we have shown that the group 7 pyridine thiolate
complexes [M (CO) -pyS)
] (M ¼ Mn, Re), act as useful synthons
to a range of complexes containing the M(CO) (pyS) fragment,
being especially useful for the rational synthesis of tetranuclear
2
6
(m
2
3
Fig. 2. Molecular structure of [Ru(CO) (SnPh )(PPh )(k2-pyS) (2) (thermal ellipsoids at
2 4 3 2 2
Fig. 1. Molecular structure of [Ru (CO) (Ph Sn) (m-pyS) ] (1) (thermal ellipsoids at 50%
2
3
3
probability). Hydrogen atoms have been omitted for clarity. Selected interatomic
50% probability). Hydrogen atoms have been omitted for clarity. Selected interatomic
ꢀ
ꢀ
ꢀ
ꢀ
distances (A) and angles ( ): Ru(1)eSn(1) 2.6457(2), Ru(2)eSn(2) 2.6576(2), Ru(1)eS(1)
.4947(6), Ru(1)eS(2) 2.5241(6), Ru(2)eS(1) 2.5214(6), Ru(2)eS(2) 2.4790(6), Ru(1)eN
1) 2.103(2), Ru(2)eN(2) 2.126(2), N(1)eRu(1)eS(1) 67.06(5), N(1)eRu(1)eS(2) 90.02(5),
S(1)eRu(1)eS(2) 84.96(2), N(1)eRu(1)eSn(1) 88.73(5), Ru(1)eS(1)eRu(2) 93.02(2).
distances (A) and angles ( ): Ru(1)eSn(1) 2.6746(5), Ru(1)eS(1) 2.4509(8), Ru(1)eN(1)
2.100(2), Ru(1)eP(1) 2.4177(7), N(1)eRu(1)eS(1) 67.44(6), N(1)eRu(1)eP(1) 90.73(6),
P(1)eRu(1)eS(1) 86.60(2), P(1)eRu(1)eSn(1) 172.96(2), N(1)eRu(1)eSn(1) 89.12(5),
S(1)eRu(1)eSn(1) 86.84(2), C(1)eRu(1)eN(1) 96.1(1), C(2)eRu(1)eC(1) 94.2(1).
2
(

A.K. Raha et al. / Journal of Organometallic Chemistry 696 (2011) 2153e2160
2157
bond lengths and angles. It has an octahedral arrangement of
ligands around the ruthenium atom, with the pyridine thiolate
ligand binding in a chelating fashion [NeRueS 67.44(6) ]. The tri-
ꢀ
N
Os (CO)10(MeCN)2
OC
OC
S
3
phenyltin and phosphine ligands lie mutually trans [P(1)eRu(1)e
SnPh
3
Os
(CO)3
Os
ꢀ
80 o
C
N
S
Sn(1) 172.96(2) ], presumably in order to minimise adverse steric
OC
Os
interactions and the two carbonyls are in a cis orientation. The
(CO)
3
Ph Sn
3
ꢀ
ꢀ
RueN and RueSn bond distances of 2.100(2) A and 2.6746(5) A,
respectively, are similar to those found in 1, while the RueS
5
ꢀ
distance of 2.4509(8) A is slightly shorter than those found in 1.
Scheme 4.
As briefly alluded to earlier, a second low yield product of the
direct reaction of Ph
3
Sn-Spy and Ru
3
(CO)12 was the cluster
angles. Hence 4 with a flattened core structure and a stabilizing ligand
attached to the convex face is unique. The pyS ligand is N-bonded to
[
Ru (CO)12(SnPh )( -pyS)] (3). In a separate experiment 1 was shown
4
3
m
to smoothly convert into 3 upon addition of further Ru
3
(CO)12 at
theruthenium atomand theS atom symmetrically bridges the Os(1)e
ꢀ
between 60and 65 C. All attemptsto characterize 3 structurally have
proved unsuccessful. The FAB mass spectrum shows the expected
parent molecular ion at m/z 1200 and further ions due to stepwise
Os(2) bond which is shorter [2.8011(12) ꢀA ] than the two unbridged
OseOs bonds [2.8601(12) ꢀA ]. The Ph Sn group occupies an equatorial
3
position on the ruthenium atom, and is disordered over two closely
adjacent positions arising from slightly different conformations of the
phenyl rings, so the SneRu distance of 2.72 ꢀA is not precise but does
appear to be significantly longer than the RueSn distances in 1 and 2.
Interestingly the RueOs(1) bond trans to the RueSn bond is not
significantly different to the RueOs(2) bond cis to it.
1
loss of 12 carbonyl ligands, while the H NMR spectrum displays only
aromatic resonances for both phenyl and pyridyl ring protons; two
multiplets centered at
9
d
7.57 (integrated to 6H) and 7.29 (integrated to
H) are attributed to the phenyl ring protons of SnPh moiety, while
6.68
3
the doublets at
d
8.58 and 8.20 (J ¼ 5.6 Hz) and the triplets at
d
and 7.25 (J ¼ 5.6 Hz), each integrating to 1H, are assigned to the ring
protons of the pyridine-2-thiolate ligands which supports the
structure proposed for 3.
3.3. Direct reaction of [Os
3 2 3
(CO)10(NCMe) ] with pySSnPh :
synthesis of an OseSn bimetallic complex
Heating a benzene solution of 1 and the labile triosmium cluster
ꢀ
3 2
[Os (CO)10(NCMe) ] at 70e75 C furnished [RuOs
3 3 3
(CO)12(SnPh )(m -
Reaction of [Os
benzene affords the triosmiumetin cluster [Os
-pyS)] (5) in 41% yield (Scheme 4). Compound 5 has been fully
3
(CO)10(NCMe)
2
] with pySSnPh
3
in refluxing
pyS)] (4) in 40% yield (Scheme 3). Spectroscopic data are very similar
to that for 3 showing that the two are structurally related. Single
crystals of 4 were grown and the structure of one of the two inde-
pendent molecules in the asymmetric unit is shown in Fig. 3. Ignoring
some twisting of the phenyl groups about the tinecarbon bond the
other independent molecule is a mirror image, and the following
discussion is based on average parameters. The core of the cluster is
3
(CO) (SnPh
9
3
)
(m
3
characterized by a combination of IR, NMR, mass spectroscopic data
and single crystal X-ray diffraction analyses.
The solid-state molecular structure of 5 is shown in Fig. 4 and
selected bond distances and angles are listed in the caption. The
molecule contains a triosmium core with three distinctly different
3
a 62-electron Os Ru butterfly, with the ruthenium atom occupying
ꢀ
osmiumeosmium interactions [Os(1)eOs(2) 2.8090(2) A, Os(1)eOs
ꢀ
a wingtip; the dihedral angle about the hinge being 156 . There are
few Os Ru butterfly precedents in the Cambridge Crystallographic
3
Database, most of the existing examples having alkyne or other
groups bridging the wingtip atoms, and much more acute dihedral
ꢀ
ꢀ
(
3) 2.8611(2) A and Os(2)eOs(3) 2.7757(2) A] ligated by nine
carbonyls, a triphenyltin and a pyridine-2-thiolate ligand. The latter
ligand caps a face of the osmium triangle; it bridges Os(1) and Os(2)
through the sulfur atom and coordinates to Os(3) through the
pyridyl nitrogen atom. The triphenyltin ligand occupies an
Fig. 3. Molecular structure of one of the independent molecules of [Os
CO)12(SnPh )( -pyS)] (4) (thermal ellipsoids at 35% probability). Only one of the two
disordered tin atoms is shown. Hydrogen atoms have been omitted for clarity. Selected
interatomic distances (A) and angles ( ) (for independent molecules 1 and 2 in each
case): Os(1)eOs(2) 2.7995(9) 2.8027(9), Os(2)eOs(3) 2.867(1) 2.870(1), Os(1)eOs(3)
3
Ru
(
3
m
3
Fig. 4. Molecular structure of [Os
3 9 3 3
(CO) (SnPh )(m -pyS)] (5) (thermal ellipsoids at 50%
probability). Hydrogen atoms have been omitted for clarity. Selected interatomic distances
ꢀ
ꢀ
ꢀ
ꢀ
(A) and angles ( ): Os(1)eSn(1) 2.6856(3), Os(1)eOs(2) 2.8090(2), Os(1)eOs(3) 2.8611(2),
Os(2)eOs(3)2.7757(2), Os(1)eS(1)2.4544(11), Os(2)eS(1)2.4009(11), Os(3)eN(1) 2.183(4),
Os(1)eOs(2)eOs(3) 61.633(6), Os(1)eOs(3)eOs(2) 59.756(6), Os(2)eOs(1)eOs(3) 58.611
(6), S(1)eOs(1)eSn(1) 86.54(3), S(1)eOs(1)eOs(2) 53.77(3), Sn(1)eOs(1)eOs(3) 146.37(1),
Sn(1)eOs(1)eOs(2) 132.21(1), N(1)eOs(3)eOs(1) 87.52(9), Os(2)eS(1)eOs(1) 70.68(3).
2.855(1) 2.870(1), Os(1)eRu(1) 2.921(2) 2.868(2), Os(2)eRu(1) 2.863(2) 2.899(2) Ru
(
2
1)eSn(1) 2.72 2.72, Os(1)eS 2.411(4) 2.400(4), Os(2)eS 2.403(4) 2.401(4), Ru(1)eN
ꢀ
.19(2) 2.20(2). Dihedral angle between Os
3
and Os
2
Ru planes 156.3, 156.1 .

2
158
A.K. Raha et al. / Journal of Organometallic Chemistry 696 (2011) 2153e2160
py
second difference relates to the positioning of the triphenyltin ligand,
S
being at a non-nitrogen bound metal atom in 5. The mode of forma-
tion of 1 and 5 remains unknown. It is tempting to suggest that the
first formed species in each case may be [M (CO) (m -pyS-SnPh )]
3 9 3 3
in which the capping group acts as a six-electron donor binding
through sulfur and nitrogen. Oxidative-addition of the tinesulfur
bond from sucha species woulddirectlyafford 5, while for ruthenium
a secondary transfer of the tin to the nitrogen bond atom followed by
(
CO)
2
Ph
P
2
(OC)
3
Os
Os
H
Ph
P
SnPh
3
Os
P
N
S
(CO)
Ph
2
3
(OC)
3
Os
Os (CO)
3
+
1
10 o
C
6
H
Os
CO)
P
(
2
Ph
2
Ph
P
2 3
cluster core degradation could afford the labile Ru(CO) (pyS)(SnPh )
fragment which dimerises to form 1.
(
CO)
Os
2
H
Ph
3
Sn
Os (CO)
3
N
S
Os
P
(
CO)
2
Ph
2
3 3 8 3 2 2
3.4. Addition of pySSnPh to unsaturated [Os (CO) {m -PPh CH P
7
6 4
(Ph)C H }(m-H)]
Scheme 5.
The electronically unsaturated 46-electron triosmium cluster
Os (CO) -PPh CH P(Ph)C }( -H)] has been shown to display
[
3
8
{
m
3
2
2
6 4
H m
equatorial position on Os(1) with the OseSn bond distance [Os(1)e
Sn(1) 2.6856(3) A] very similar to those found in related triosmium
a rich and varied chemistry [54]. In the context of this work two of
its reactions are noteworthy. Thus, addition of pyridine-2-thiol
ꢀ
clusters [17e19,27e30]. The osmiumenitrogen [Os(3)eN(1) 2.183
3 8
proceeds at room temperature to give thiolate-bridged [Os (CO) (m-
ꢀ
ꢀ
(
2
4) A] and osmiumesulfur [Os(2)eS(1) 2.401(1) A and Os(1)eS(1)
.454(1) A] distances are within the usual ranges [50,53]. Consid-
dppm)(m-H)(m-Spy)] (6) [55], in which the pyS ligand binds only
ꢀ
through sulfur, together with a second product, [HOs (CO) {m3-
3
8
2
ering the pyridine-2-thiolate ligand serves as five-electron donor, 5
is an 48-electron cluster with three metalemetal bonds. Spectro-
scopic data are consistent with the solid-state structure. The
PPh CH P(Ph)C H }(
6 4
k
-pyS)] [55], containing an open array of
osmium atoms and a chelate N,S-pyS ligand. It also reacts at room
temperature with triphenyltin to afford [Os (CO) (SnPh ){m3
2
2
3
7
3
-
1
aromatic region of the H NMR spectrum shows two doublets and
2 2 6 4 2
PPh CH P(Ph)C H }(m-H) ] resulting from oxidative-addition of the
two triplets with a relative intensity of 1:1:1:1 due to the ring
protons of pyridine-2-thiolate ligand and two multiplets integrated
to 15H for the phenyl protons of the triphenyltin ligand. The FAB
mass spectrum exhibits the molecular ion at m/z 1283 and other
ions due to the sequential loss of nine carbonyl ligands.
3 8 2 2
tinehydride bond [17]. Reaction of [Os (CO) {m3-PPh CH P(Ph)
C H }(m-H)] with pySSnPh3 in refluxing toluene resulted in the
6
4
formation of two osmiumetin clusters [Os (CO) (
3
8
m
-pyS)(
4
m
m
-H)(
m
-
-
dppm)] (6) and [Os (CO) (SnPh ){
3
7
3
m
-Ph PCH P(Ph)C H }( -pyS)(
2
2
6
m
H)] (7) in 29 and 38% yield, respectively (Scheme 5). Cluster 6 has
previously been reported and was identified by comparison of its
spectroscopic data with the literature values [55].
The difference inisolated products fromthe reactions of Ru
3
(CO)12
and [Os (CO)10(MeCN) ] with Ph Sn-Spy reflects the well-known
3
2
3
enhanced stability of osmiumeosmium vs. rutheniumeruthenium
bonds. Thus in both reactions the oxidative-addition of the tinesulfur
bond is facile but for osmium the triosmium unit remains intact. A
The new cluster 7 was characterized by a combination of spec-
troscopic data and an X-ray crystal structure, the results of which
are shown in Fig. 5 with the caption containing selected interatomic
Fig. 5. Molecular structure of [Os
3
(CO)
7
(SnPh
3
){
m
-Ph
2
PCH
2
P(Ph)C
6
H
4
}(
m
-pyS)(
m
-H)] (7) (thermal ellipsoids at 50% probability). Hydrogen atoms have been omitted for clarity.
ꢀ
ꢀ
Selected interatomic distances (A) and angles ( ): Os(3)eSn(1) 2.6731(4), Os(1)eOs(2) 2.9254(3), Os(2)eOs(3) 3.344(1), Os(1)eS(1) 2.4643(12), Os(3)eS(1) 2.474(1), Os(3)eN(1)
ꢀ
2
8
.113(4), Os(1)eC(11) 2.167(4), Os(1)eP(1) 2.3282(12), Os(2)eP(2) 2.3533(11), Os(1)eOs(2)eOs(3) 55.2 , Os(1)eS(1)eOs(3) 108.11(4), C(11)eOs(1)eS(1) 85.2(1), C(11)eOs(1)eOs(2)
9.6(1), P(1)eOs(1)eS(1) 162.25(4), P(1)eOs(1)eOs(2) 90.44(3), N(1)eOs(3)eS(1) 66.8(1), S(1)eOs(3)eSn(1) 90.56(3), N(1)eOs(3)eSn(1) 86.8(1).

A.K. Raha et al. / Journal of Organometallic Chemistry 696 (2011) 2153e2160
2159
3 7 3 2 2 6 4
Fig. 6. Schematic structure (drawn without H atoms, except hydride) and selected molecular orbitals of [Os (CO) (SnPh ){m-Ph PCH P(Ph)C H }(m-pyS)(m-H)] (7).
distances and angles. It consists of an open triosmium cluster with
The mode of formation of 7 is similar to that of 5 formed upon
addition of Ph Sn-pyS to [Os (CO)10(MeCN) ] but now the cleaved
pyridine thiolate ligand bridges only two metal atoms; probably
a result of the sterically demanding nature of the deprotonated
dppm ligand. A further difference is the positioning of the triphe-
nyltin ligand which in 7 is bound to the N-bound metal centre.
two quite different osmiumeosmium interactions, Os(1)eOs(2)
3
3
2
ꢀ
ꢀ
2
.9254(3) A and Os(2)eOs(3) 3.344(1) A. The latter is much longer
than expected is probably bridged by the hydride (not located)
1
a supposition supported by the H NMR spectrum [
2
d
ꢁ16.6 (J ¼ 16.4,
.8 Hz)], the two quite different coupling constants suggesting that
the hydride is not located at a similar distance from both phos-
phorus nuclei. The pyS ligand bridges the open Os(1)eOs(3) edge
through the sulfur atom while it coordinates with Os(3) by the ring
nitrogen thus forming a four-membered chelate ring. The triphe-
nyltin ligand is equatorially bonded to Os(3). The deprotonated
dppm ligand spans the Os(1)eOs(2) edge such that it is equatorially
bonded to Os(1) using one phosphorus atom while axially coordi-
nated to Os(2) through the other phosphorus atom to facilitate the
bonding of one of the phenyl rings to Os(1). Spectroscopic data are
in accord with the solid-state structure. The 31P{ H}NMR spectrum
4. Conclusions
This work has established pyridine-2-thiolate-triphenyltin,
Ph Sn-Spy, as a source of both triphenyltin and pyridine-2-thiolate
3
ligands via the facile sulfuretin bond cleavage. While in all cases
triphenyltin binds in a monodentate fashion, the precise nature of
the products obtained varies as a function of the different binding
modes of the pyridine-2-thiolate ligand, being found in chelating,
bridging and face-capping coordination modes. This suggests that
not only will Ph Sn-Spy serve as a useful reagent towards the
synthesis of tin-containing transition metal clusters but related
compounds differing in the nature of the substituent on sulfur are
likely to provide routes into further novel cluster types. An aim of
our work in this area is the high yield synthesis of clusters with
specific transition metal to tin ratios and geometries for use as
precursors towards nano-particulate catalysts and the ability to
control these variables in a clear and systematic way is key to the
success of this goal.
1
shows two resonances at
d
ꢁ5.5 and ꢁ28.5 indicating the presence
3
of two non-equivalent phosphorus atoms while the FAB mass
spectrum exhibits the molecular ion at m/z 1611 and other ions due
to the sequential loss of seven carbonyl ligands.
ꢀ
The Os(2)eOs(3) distance of 3.344 A is long in comparison to
conventional osmiumeosmium single bond distances and thus in
order to get more information about this interaction we have per-
formed DFT calculations on 7 (Supporting Information). A good
ꢀ
agreement between the experimental and calculated (3.353 A) Os
(
2)eOs(3) distance is found. An electronic structure analysis shows
that a direct Os(2)eOs(3) interaction is not present and the two
metal centres are rather interacting through the hydride atom.
According to natural bonding orbital (NBO) method [47], the
hydride atom is binding Os(2) and Os(3) by a delocalizing interac-
tion between its lone pair and two anti-bonding orbitals of Os(2)
and Os(3). NBO gives a negative charge of ꢁ0.278 and ꢁ0.201 to
these two atoms, respectively, while the charge on the hydride
atom is ꢁ0.184. A similar type of interaction is also obtained in the
canonical molecular orbital description, where the HOMO-1 shows
an interaction centered on the hydride atom between a Os(2)eCO
anti-bonding orbital and a Os(3)eSn bonding orbital (Fig. 6).
Acknowledgements
This research has been sponsored by the Ministry of Science and
Information & Communication Technology, Government of the
People’s Republic of Bangladesh. We thank Dr Tania Groutso,
University of Auckland, for collection of X-ray data.
Appendix A. Supplementary data
Text, tables and cif files giving details of the X-ray crystallo-
graphic structure determinations together with computational

2160
A.K. Raha et al. / Journal of Organometallic Chemistry 696 (2011) 2153e2160
details with selected results for 7. Cif files are also available free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge, CB2 1FZ, U.K.: fax: þ44 1223 336033; e-mail: deposit@
ccdc.cam.ac.uk) as supplementary publications: CCDC Nos.
[30] S.E. Kabir, A.K. Raha, M.R. Hassan, B.K. Nicholson, E. Rosenberg, A. Sharmin,
L. Salassa, Dalton Trans. (2008) 4212.
[
31] S. Ghosh, R. Pervin, A.K. Raha, S.E. Kabir, B.K. Nicholson, Inorg. Chim. Acta 362
2009) 4226.
[32] G. Hogarth, S.E. Kabir, E. Nordlander, Dalton Trans. 39 (2010) 6153.
(
[
[
33] B.F.G. Johnson, J. Lewis, D.A. Pippard, J. Chem. Soc., Dalton Trans. (1981) 407.
34] J.A. Clucas, D.F. Foster, M.M. Harding, A.K. Smith, J. Chem. Soc., Chem.
Commun. (1984) 949.
7
95531e795535 for 1, 2, 4, 5 and 7, respectively.
Supplementary information associated with this article can be
found in the online version at doi:10.1016/j.jorganchem.2010.11.
22.
[35] E.W. Abel, D.B. Brady, J. Chem. Soc. (1965) 1192.
[
[
36] R.C. Pollar, The Chemistry of Organotin Compounds (1970).
37] W. Henderson, J.S. McIndoe, B.K. Nicholson, P.J. Dyson, J. Chem. Soc., Dalton
Trans. (1998) 519.
0
[
38] R.H. Blessing, Acta Crystallogr., Sect. A A51 (1995) 33.
References
[39] G.M. Sheldrick, SHELXL-97, Program for Refinement of Crystal Structures.
University of Göttingen, Germany, 1997.
[
[
[
1] S. Hermans, B.F.G. Johnson, J. Chem. Soc., Chem. Commun. (2000) 1955.
2] J.M. Thomas, D.W. Lewis, Angew. Chem. Int. Ed. 44 (2005) 6456.
3] J.M. Thomas, R. Raja, B.F.G. Johnson, S. Hermans, M.D. Jones, T. Khimyak, Ind.
Eng. Chem. Res. 42 (2003) 1563.
[40] L.J. Farrugia, WinGX, Version 1.70.01, University of Glasgow, UK.
[41] L.J. Farrugia, J. Appl. Crystallogr. 32 (1999) 837.
[42] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb,
J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant,
J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi,
G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara,
K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo,
J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi,
C. Pomelli, J. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador,
J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain,
O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Forestman, J.V. Ortiz,
Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko,
P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng,
A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen,
M.W. Wong, C. Gonzales, J.A. Pople, Gaussian 03. (Revision D.01). Gaussian
Inc., Wallingford CT, 2004.
[43] A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
[44] C. Lee, W. Yang, R.G. Parr, Phys. Rev.B: Condens. Matter 37 (1988) 785.
[45] P.J. Hay, W.R. Wadt, J. Chem. Phys. 82 (1985) 270.
[46] A.D. McLean, G.S. Chandler, J. Chem. Phys. 72 (1980) 5639.
[47] A.E. Reed, L.A. Curtiss, F. Weinhold, Chem. Rev. 88 (1988) 899.
[48] C.J. Cardin, D.J. Cardin, M.A. Convery, Z. Dauter, D. Fenske, M.M. Devereux,
M.B. Power, J. Chem. Soc., Dalton Trans. (1996) 1133.
[49] K.M. Hanif, M.S. Islam, S.E. Kabir, K.M.A. Malik, M.A. Miah, N. Wakelin, J. Chem.
Crystallogr. 33 (2003) 859.
[
4] J.M. Thomas, B.F.G. Johnson, R. Raja, G. Sankar, P.A. Midglcy, Acc. Chem. Res. 36
(
2003) 20.
[
[
[
[
[
5] B.F.G. Johnson, Top. Catal. 24 (2003) 147.
6] R. Srinivasan, B.H. Davis, Platinum Met. Rev. 36 (1992) 151.
7] R. Bruce, L.C. Garla, J. Catal. 71 (1981) 360.
8] T. Fujikawa, F.H. Ribciro, G.A. Somorjai, J. Catal. 178 (1998) 58.
9] R. Bruce, J. Catal. 71 (1981) 348.
[
[
10] M.S. Holt, W.L. Willson, J.H. Nelson, Chem. Rev. 89 (1989) 11.
11] S. Hermans, R. Raja, J.M. Thomas, B.F.G. Johnson, G. Sankar, D. Gleeson, Angew.
Chem. Int. Ed. 40 (2001) 1211.
12] G.W. Hurber, J.W. Shabaker, J.A. Dumesic, Science 300 (2003) 2075.
13] B.F.G. Johnson, S.A. Raynor, D.B. Brown, D.S. Shephard, T. Mashmeyer,
J.M. Thomas, S. Hermans, R. Raja, G. Sankar, J. Mol. Catal. A: Chem. 182e183
[
[
(
2002) 89.
[
14] A. Hungria, R. Raja, R.D. Adams, B. Captain, J.M. Thomas, P.A. Midgley,
V. Golvenko, B.F.G. Johnson, Angew. Chem. Int. Ed. 45 (2006) 969.
15] K. Burgess, C. Guerin, B.F.G. Johnson, J. Lewis, J. Organomet. Chem. 295 (1985) C3.
16] W.K. Leong, R.K. Pomeroy, R.J. Batchelor, F.W.B. Einstein, C.F. Compana,
Organometallics 15 (1996) 1582.
[
[
[
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.
[
[
[
18] R.D. Adams, B. Captain, Z. Lei, Organometallics 25 (2006) 4183.
19] R.D. Adams, B. Captain, Z. Lei, Organometallics 25 (2006) 2049.
20] R.D. Adams, D.A. Blom, B. Captain, R. Raja, J.M. Thomas, E. Trufan, Langmuir 24
[50] S. Ghosh, S.E. Kabir, S. Pervin, A.K. Raha, G.M.G. Hossain, D.T. Haworth,
S.V. Lindeman, T.A. Siddiquee, D.W. Bennett, L. Salassa, H.W. Roesky, J. Chem.
Soc., Dalton Trans. (2009) 3510.
(
2008) 9223.
[
[
[
[
21] R.D. Adams, B. Captain, E. Trufan, J. Organomet. Chem. 693 (2008) 3593.
22] R.D. Adams, E.M. Boswell, B. Captain, M.A. Patel, Inorg. Chem. 46 (2007) 533.
23] R.D. Adams, B. Captain, E. Trufan, J. Clust. Sci. 18 (2007) 642.
24] R.D. Adams, B. Captain, M.A. Patel, M. Johansson, J.L. Smith Jr., J. Am. Chem.
Soc. 127 (2005) 488.
25] R.J. Hall, P. Serguievski, J.B. Keister, Organometallics 19 (2000) 4499.
26] F.W.B. Einstein, R.K. Pomeroy, A.C. Willis, J. Organomet. Chem. 3111 (1986) 257.
27] D.J. Cardin, M.F. Lappert, J. Chem. Soc., Chem. Commun. (1966) 506.
28] D.J. Cardin, S.A. Keppie, M.F. Lappert, J. Chem. Soc., A (1970) 2594.
29] J.L. Greàt-Morales, J.M. Fernàndez-G, Organometallics 23 (2004) 3840.
[51] S. Ghosh, K.N. Khanam, M.K. Hossain, G.M.G. Hossain, D.T. Haworth,
S.V. Lindeman, G. Hogarth, S.E. Kabir, J. Organomet. Chem. 695 (2010)
1146.
[52] S. Ghosh, K.N. Khanam, G.M.G. Hossain, D.T. Haworth, S.V. Lindeman,
G. Hogarth, S.E. Kabir, New J. Chem. 34 (2010) 1875.
[53] A.J. Deeming, M.N. Meah, N.P. Randle, K.I. Hardcastle, J. Chem. Soc., Dalton
Trans. (1989) 2211.
[54] S.E. Kabir, G. Hogarth, Coord. Chem. Rev. 253 (2009) 1285.
[55] S.E. Kabir, K.M.A. Malik, E. Molla, M.A. Mottalib, J. Organomet. Chem. 616
(2000) 157.
[
[
[
[
[