Synthesis of a one-dimensional coordination polymer containing pendant hydrosulfide groups

Article abstract of DOI:10.1039/b908304a

In view of the recent interest in compounds containing M-SH units, an organotin hydrosulfide compound, Me₂Sn(SH)(O₂CMe) (1) was prepared by controlled hydrolysis of the diorganotin thioacetate. Under similar mild hydrolytic condition

Full text of DOI:10.1039/b908304a

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Synthesis of a one-dimensional coordination polymer containing pendant
hydrosulfide groups†
Jyotsna Chaturvedi,a Subrato Bhattacharya*a and M. Nethajib
Received 19th May 2009, Accepted 11th August 2009
First published as an Advance Article on the web 24th August 2009
DOI: 10.1039/b908304a
In view of the recent interest in compounds containing M–SH units, an organotin hydrosulfide
compound, Me2Sn(SH)(O2CMe) (1) was prepared by controlled hydrolysis of the diorganotin
thioacetate. Under similar mild hydrolytic conditions the corresponding benzoate could not be isolated.
Instead, the thiobenzoate complex, Me2Sn(SOCPh)2 (3) was obtained in excellent yields indicating that
there was no hydrolysis. Both 1 and 3 were characterized by X-ray crystallography. Some properties of
the polymeric compound 1, such as spectral, electrical conductivity and NLO response were also
studied. The reactivity and properties were explained using density functional calculations.
have attempted to carry out the hydrolysis in acidic medium.
Introduction
A reaction of Me2SnO with thioacetic acid was performed to
Coordination polymers built up from organic ligands and in-
prepare Me2Sn(SOCMe)2 which was then treated with dil. HCl
organic moieties have developed into an important class of
in equimolar proportions in methanol. The reaction product was
solid-state materials. Such materials often form porous metal–
the well known trimeric diorganotin sulfide, (Me2SnS)3. In order
organic frameworks (MOFs).1–6 Over the past few years MOFs
to make the hydrolytic conditions milder we then tried to carry out
have attracted attention in view of their potential for the design
the complex formation reaction in the presence of a Lewis acid.
of multifunctional materials.7,8 Though extensive efforts have
Interestingly, the reaction was found to take a different route and
been devoted to the preparation of new oxygen-based MOFs,9
a complex with the desired functionality was formed (Scheme 1).
analogous sulfur based materials are scanty in the earlier literature.
Such materials are expected to be promising candidates for the
integration of porosity with electronic and/or optical properties.6
Metal complexes containing hydrosulfido ligands have, however,
recently been used as precursors for metallorganic frameworks
and early-late heterobimetallic complexes.10
Hydrosulfido complexes of the main group metals are scarce. A
monomeric aluminium compound with two terminal SH groups11
Scheme 1
have been prepared by Roesky et al. which they have lithiated12
and very recently utilized in synthesizing bimetallic complexes.13
A reaction of Me2SnO and thioacetic acid in the presence of
a Lewis acid such as InCl3 or FeCl3 in methanol resulted in
1. The plausible mechanism is displayed in Scheme 2. Possibly,
Roper et al. have stabilized a terminal Sn–SH moiety for the first
time by adequate steric protection using bulky ligands.14 We have
very recently, reported our studies on various hydrolytic reactions
the reaction of dimethyltin oxide with thiocarboxylic acid is
of a diorganotin thioacetate with the hope of preparing organotin
a step wise one and the initial steps are the same in both
hydrosulfides.15 However, all of our attempts were unsuccessful.
cases (HCl catalyzed/Lewis acid mediated). In the first step
In this paper we report on a novel route for the synthesis of a one
dimethyl(hydroxo)tin thioacetate is formed. The presence of an
dimensional organotin polymer containing pendant SH groups.
acid in (HCl or In3+) induces a partial positive charge on
the carbonyl carbon (of the thioacetate group) which is then
attacked by the hydroxyl group leading to the formation of
dimethyl(hydrosulfido)tin acetate (in the case where a Lewis acid
is used). However, in the presence of HCl, deprotonation of acetic
acid (step iii) is not favored and Sn–S–Sn bonds are formed
resulting in the trimeric dimethyltin sulfide (4). Formation of
Sn–S–Sn bonds is in fact, a general problem associated with the
preparation of hydrosulfido complexes. Mononuclear hydrosul-
fido complexes initially formed are further aggregated leading to
the formation of polynuclear sulfido complexes or insoluble metal
sulfides.14,16,17 Encapsulation by sterically hindering bulky groups
is expected to provide sufficient inertness of the tin centre so that
the decomposition in the form of tin-sulfide should be avoided
and the Sn–SH unit should be obtainable.18 In compound 1 the
Results and discussion
Syntheses
As described already our recent attempts to prepare hydrosulfide
complexes of organotin(IV) by hydrolyzing diorganotin thioac-
etate under neutral/basic media were unsuccessful. Now we
aDepartment of Chemistry, Banaras Hindu University, Varanasi, 221005,
India. E-mail: s_bhatt@bhu.ac.in
bDepartment of Inorganic and Physical Chemistry, Indian Institute of
Science, Bangalore, India
† CCDC reference numbers 725580 and 725581. For crystallographic data
in CIF or other electronic format see DOI: 10.1039/b908304a
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Scheme 2
acetate ligand bridges between two tin centers forming a linear
chain which is sufficiently rigid to disallow formation of Sn–S–Sn
linkages.
On the other hand, when thiobenzoic acid was used in place of
thioacetic acid the corresponding bis-thiobenzoate (3) is formed
which is quite inert and there is no effect on addition of InCl3. We
have tried to follow the reactions by 1H NMR spectroscopy. When
a solution of thioacetic acid was added to Me2SnO the resulting
reaction mixture showed two signals due to the methyl groups of
Me2Sn and SCOMe moieties respectively at 0.96 and 2.41 ppm.
The intensity of the signal at 0.96 ppm was observed to increase
with time as expected (Me2SnO has very low solubility in methanol
while the product is quite soluble). After attainment of equilibrium
(in ~1.5 h) addition of InCl3 resulted in the appearance of a small
peak due to the SH proton at 2.01 ppm whose intensity increased
with time until equilibrium was reached. On the other hand in the
case of the reaction with thiobenzoic acid no change was observed
before and after the addition of InCl3.
Scheme 3
Solid state structures of Me2Sn(SH)(O2CMe) (1) and
Me2Sn(SOCPh)2 (3). The complex Me2Sn(SH)(OOCMe) (1)
crystallizes in the orthorhombic crystal system with the Pnma
space group. The thermal ellipsoid plot is given in Fig. 2.
To understand the differences in reactivity of thioacetate and
thiobenzoate ligands we have carried out density functional calcu-
lations on Me2Sn(OH)(SOCMe) (2A) and Me2Sn(OH)(SOCPh)
(2B). In the optimized structures the thioacetate is monodentate
˚
through sulfur (Sn ◊ ◊ ◊ O = 2.92 A) while the thiobenzoate ligand
˚
is bidentate (Sn–O = 2.52 A) respectively in 2A and 2B. However,
the NBO charges19 on various atoms of 2A are not much different
from those on the corresponding atoms of 2B. The difference in
reactivity of the compounds originates from the nature and energy
levels of the lowest unoccupied orbitals (LUMO) (Fig. 1).
Fig. 2 Thermal ellipsoid plot of 1 (two tin atoms are shown to clarify
bridging by the O1¢ atom). Selected metric data: Sn1–C1 2.098(4), Sn1–S1
2.37(1), Sn1–O1 2.392(4), Sn1–O2 2.154(3), Sn1–O1¢ 2.779, C1–Sn1–C1
140.4(2), C1–Sn1–O2 108.75(12), C1–Sn–O2 97.22(13).
The Sn1 atom appears to be six-coordinated, however, the
geometry around the metal centre is highly deviated from that
of a regular octahedron and closer to a trapezoidal bipyramid
due to the small bite angle of the acetate ligand. A large number
of diorganotin compounds have skewed trapezoidal bipyramidal
geometry around the tin center.21 A recent study22 using the Cam-
bridge structural database has revealed that in skew trapezoidal
molecules the cis- and trans-C–Sn–C angles range between 102–
110◦ and 180–145◦ respectively. While the same in the transition
state of the cis–trans pathway ranges between 120◦ and 134◦. The
O–Sn–O angle in frozen transition states are > 160◦ < 170◦.22
Since the C1–Sn–C1 angle in 1 is 140.4◦, and the O1–Sn1–O1¢
angle is 138.85◦ the geometry of 1 fits into none of these three
categories.
Fig. 1 LUMO of 2A and 2B (Orbitals plotted at a contour value of 0.05).
In 2A the LUMO is CO p* which is attacked by the OH group
as shown in Scheme 2. On the other hand the same orbital (CO
p*) is of much higher energy (LUMO +5) in 2B because of the
stabilization of the CO p orbital. The LUMO in 2B is the Ph–C
p orbital which is quite low lying and indicates the contribution
20
=
of a canonical form with the Ph C bond (Scheme 3). The same
also supports the stabilization of the CO p orbital by conjugation.
Thus in 2B there is no orbital at the carbonyl carbon of suitable
energy and symmetry which could be attacked by the OH group.
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The acetate ion exhibits an asymmetric mode of bonding with
Though the geometry around tin in 3 may also be described as
skewed trapezoidal bipyramidal, the two thiocarboxylates groups
are not really coplanar (interplanar angle is 4.44◦). Moreover, all
the four C–Sn–S angles range between 105.26◦ and 109.44◦ which
are very close to the ideal tetrahedral angle. However, the C–Sn–C
angle is quite wider than the tetrahedral angle but does not fit
into the skewed trapezoidal model.22 The deviation of the C–Sn–C
angle is also due to the weak Sn ◊ ◊ ◊ O bonds capping the two faces
of the tetrahedron.26,30
˚
a very long Sn1–O1¢ bond (2.779 A). This is much longer than the
˚
sum of the covalent radii of Sn and O (2.14 A) but quite shorter
˚
than the sum of their van der Waals’ radii (3.69 A). It may be
noted that almost all diorganotin carboxylates exhibit asymmetric
bonding of the carboxylate ligands. The longer Sn–O bond usually
ranges from 2.45 to 2.55 A.23–26 Amongst the monomeric diorgan-
˚
otin carboxylates, the longest Sn–O bond has been reported to
27
˚
be 2.696 A in the case of hexamethylenetin bis(chloroacetate).
A still longer Sn–O1¢ distance in 1 is due to the fact that O1¢
˚
has a closer contact (2.392 A) with another tin atom forming a
Electronic absorption spectra
bridge between two Sn centers. The structure is thus comparable
to the polymeric tin carboxylates.28 A better description of the
geometry therefore, can be made by considering the longer Sn–O
bond as a weak interaction only. The geometry around tin can
be described as trigonal bipyramidal. The O1–Sn–O2 angle being
170.24◦ places the two oxygen atoms at the axial positions. Sn1 is
slightly tipped above (by only 0.179) the plane constituted by C1,
C1¢ and S1 atoms. The three O atoms, S1 and Sn1 lie in a plane
which is perpendicular to the C1, C1¢, S1 plane. The deviation
in the C–Sn–C angle from the expected value of 120◦ may be
attributed to the capping of the C1–C2–O2 face by the O1 atom.
It is interesting to note that all the O–Sn–OC units lie in the
same plane constructing a straight polymeric chain (Fig. 3). The
The electronic absorption spectra of 1 and 3 were recorded
in DMSO and CHCl3 solutions respectively. In the case of 1
absorption bands were observed at 304 nm and 238 nm, while
in the case of 3 these bands arise at 300, 264 and 212 nm. Such
bands may arise because of the intra-ligand or ligand to metal
charge transfers. Time-dependent density functional calculations
reveal that in the case of 1 the calculated absorptions at 308 nm
and 249 nm arise because of the ligand to metal charge transfers
involving HOMO-4 to LUMO and HOMO to LUMO of the
molecule (Fig. 6). In the case of 3 the calculated absorptions at 304,
267 and 214 arise due to intra-ligand n→p* transitions involving
HOMO-2 to LUMO+1, HOMO to LUMO+1 and HOMO-1 to
LUMO+3 of the molecule (Fig. 7).
˚
nearest intermolecular Sn–S distance in a chain is 4.438 A while
˚
that between the two chains is 5.325 A.
Compound 3 crystallizes in discrete molecular units (Fig. 4)
It may be noted that the only other structurally characterized
tin(IV) bis(thiocarboxylate) which we have reported earlier29
has a distorted octahedral environment around tin. The two
thiobenzoate ligands in 3 bind bidentately with Sn–O distances
of 2.649 A and 2.720 A which are significantly longer than the
corresponding distance in the earlier reported Cl2Sn(SOCPh)2.29
The difference in the two Sn–O bond lengths in 3 arises possibly
due to the weak intermolecular Sn ◊ ◊ ◊ O interaction. (Fig. 5).
Non-Linear optical properties
In comparison with the standard p-nitroaniline (29.56 ¥ 10-30 esu)
the first static hyperpolarizability in a methanolic solution of 1
was found to be 26.73 ¥ 10-30 esu, thereby revealing a moderate
non-linear optical response for this compound. This was further
substantiated by theoretical calculations using the finite field
perturbation method i.e., by double numerical differentiation of
energies. Hyperpolarizability is given by the coefficients in the
˚
˚
Fig. 3 Orientation of the polymeric chains of 1 in the lattice.
Fig. 4 Thermal ellipsoid plot of 3. Selected metric data: Sn–C1 2.112(4), Sn–S1 2.4918(12), Sn–S2 2.4923(12), Sn–O1 2.720, Sn–O2 2.649, C1–Sn–C2
129.62(19), C1–Sn–S1 109.44(14), S1–Sn–S2 90.68(4), O1–Sn–O2 149.61, O1–Sn–S1 59.37, O1–Sn–S2 1.
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Fig. 5 A pair of molecules of 3 showing intermolecular interactions.
Fig. 6 Selected orbital transitions for 1 (orbital contour value 0.05).
Taylor series expansion31 of the energy in the external electric
field. If the external electric field is weak and homogeneous the
expansion becomes:
E = E◦ - maFa - 1/2aabFaFb - 1/6babg FaFbFg + ........
Where E◦ is the energy of unperturbed molecules, Fa is the field
of origin, ma, aab and babg are the components of dipole moment,
polarizability and the first hyperpolarizability respectively. The
mean first hyperpolarizability is defined as,32
(1)
Fig. 7 Selected orbital transitions for 3 (orbital contour value 0.05).
The solvent parameters used were of methanol. The bo value
calculated for the monomeric unit 1 was found to be 5.02 ¥ 10-30 esu
in methanol but the same for a trimeric chain was calculated to be
409.41 ¥ 10-30 esu. It is interesting to note that the monomeric unit
of 1 does not possess a chiral center, however, the presence of the
lone pair of electrons on the oxygen atoms are rather delocalized
over the molecular skeleton which is possibly responsible for the
NLO response. In the case of 3 the molecules are discrete (except
for the weak O–Sn interactions which couples up two molecules
together) and the calculated bvec value was only 4.72 ¥ 10-30esu.
Computed hyperpolarizability values of 1 and 3 and its compo-
nents are shown in Table 1. Compared with that of p-nitroaniline
(pNA) computed at the same level of theory the trimeric unit of 1
b0=(bx +by +bz )1/2
,
2
2
2
where the bx, by and bz components can be described by,
bx= bxxx +bxyy +bxzz
by= byyy +byxx +byzz
bz= bzzz +bzxx +bzyy
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Table 1 Computed dipole moment (m) and hyperpolarizabilities
Table 2 Crystal data and structure refinement of 1 and 3
System
(m)
bx
by
bz
b0
1
3
pNA
7.53
1.57
9.42
0.85
-13.70
0.03
1.72
0.49
-3.52
13.72
5.02
Empirical formula
M
C4H10O2S1Sn
240.90
293
Orthorhombic
Pnma
9.310(3)
7.671(3)
11.045(4)
90
788.8(5)
4
3.428
R1 = 0.0282
wR2 = 0.0651
R1 = 0.0364
R2 = 0.0688
0.959
C16H16O2S2Sn
423.11
153
Monoclinic
P21/c
10.546 (3)
14.516(4)
12.049(4)
107.702(4)
1757.2(9)
4
1
Monomeric
Trimeric
3.14
350.80 -40.36 207.20 409.41
-0.53 -4.69 -0.056 4.72
T/K
3
Crystal system
Space group
˚
a/A
˚
showed an excellent first order non linear optical response while
in the case of 3 only a weak hyperpolarizability was calculated.
b/A
˚
c/A
b/◦
V/A
Z
3
˚
Pressed pellet conductivity
m (Mo-Ka)/mm-1
Final R indices
[I > 2s(I)]
1.692
The pressed pellet electrical conductivity value of 1 was deter-
mined to be 8.13 ¥ 10-9 S cm-1 at room temperature (38 ◦C) which
was increased to 1.14 ¥ 10-7 S cm-1 at 60 ◦C. The variation of
electrical conductivity with temperature for complex 1 (Fig. 8)
reveals that the compound is a semiconductor with a band gap of
1.01 eV.
R1 = 0.0370
wR2 = 0.0868
R1 = 0.0399
R2 = 0.0882
1.300
R indices(all data)
GOF on F2
storage oscilloscope. Methanol was the solvent of choice and
p-nitroaniline was used as the external reference.
Single crystal X-ray data of 1 and 3 were collected at room
temperature on Bruker SMART APEX CCD diffractometers
using graphite monochromated MoKa radiation (l = 0.71073
˚
A). Data integration and reductions were processed with SAINT+
software.36 Structures were solved by the direct method and then
refined on F2 by the full matrix least square technique with
SHELX-97 software37 using the WinGX program package.38
A
summary of crystallographic data and the structure solution are
given in Table 2.
Computational details
Optimized molecular geometries were calculated using the
B3LYP39,40 exchange–correlation functional. The effective core
potential (ECP) standard basis set LANL2DZ was utilized for Sn
atoms while the 6-31g** basis set was used for C, H, O and S atoms.
The optimized structures of the complexes were used for molecular
orbital analyses. The energies and intensities of the 30 lowest-
energy spin allowed electronic excitations were calculated using the
TD-DFT at the same level of theory with the polarized continuum
model (PCM).41,42 The solvent parameter was that of methanol.
The first static hyperpolarizability (b0) for both the complexes
where calculated by using the finite field perturbation method
by implementing the PCM model. X-ray coordinates were used
for calculation of electronic excitations and hyperpolarizability.
Natural bond orbital (NBO) calculations were performed using
the LANL2DZ(d,p) basis set for all the atoms. All theoretical
calculations were performed using the GAUSSIAN 03 W set
of programs.43 Molecular orbital plots were generated using the
program MOLDEN.44
Fig. 8 Plot of log conductivity of 1 vs 1/T.
Experimental
All solvents were of reagent grade and were purified by
standard methods.33 Anhydrous InCl3, thiobenzoic acid (98%)
and dimethyltin(IV) oxide (all Aldrich) were used as received.
Thioacetic acid (96%, Aldrich) was distilled before used.
IR spectra were recorded using Perkin-Elmer RX-1, FT-IR
spectrometer and Varian-3100 FTIR instruments. NMR spectra
were obtained using a JEOL AL300 FT NMR spectrometer.
Electronic absorption spectra were recorded using a Shimadzu
UV-1700 PharmaSpec Spectrophotometer. Pressed pellet electri-
cal conductivity was recorded on a Kiethley-236 source measure-
ment unit by employing a conventional two-probe technique in
the temperature range 311–333 K. The first hyperpolarizability of
the complex 1 was measured by hyper-Rayleigh scattering using
a Q-switched Nd:YAG Laser at 1064 nm.34,35 The laser beam was
focused 2–3 cm away from a cylindrical sample cell placed in
front of a monochromator. No collection optics were used. The
dispersed second harmonic scattered light signal at 532 nm was
collected through the monochromator using a photomultiplier
tube, averaged over 512 laser shots and stored in a digital
Synthesis of [Me2Sn(OOCMe)(SH)] (1). To a stirred suspen-
sion of dimethyltin(IV) oxide (0.165 g, 1 mmol) in methanol (10 ml)
was added a methanolic (10 ml) solution of thioacetic acid (0.152 g,
2 mmol). The reaction mixture was stirred at 18 ◦C for 30 min. A
methanolic solution of InCl3 (0.110 g, 0.5 mmol) was then added
and the reaction mixture stirred for 4 h. The solvent was then
evaporated under reduced pressure and the residue was extracted
with CHCl3 (20 ml). The precipitate was filtered off and solvent
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from the filtrate was evaporated under reduced pressure. The
colourless product was dried under vacuum for 2 h. Recrystallized
by slow evaporation of a dilute chloroform solution. (61% yield);
Mp: 189 ◦C. Anal. Calcd for SnC4H10O2S: C, 19.94; H, 4.18,
found: C, 19.67; H, 4.10. 1H NMR (CDCl3, ppm): 1.19 (6H, Me),
2.45 (3H, Me). IR (KBr, cm-1):1557 n(CO), 465 n(Sn–O) and
279 n(Sn–C).
Acknowledgements
Authors are grateful to Prof. P. K. Das and Mr. Ravindra Pandey
of the Indian Institute of Science, Bangalore for measurement
of NLO properties. Thanks are due to the coordinator, SAP,
Department of Chemistry, Banaras Hindu University and the
coordinator X-ray diffraction facility, University of Hyderabad
respectively for computational facility and X-ray data collection
of compound 3. Financial assistance (to S. B.) from the UGC and
the CSIR, India is also gratefully acknowledged.
Attempted synthesis of Me2Sn(SH)(O2CPh) 1A [Synthesis of
Me2Sn(SOCPh)2 (3)]. A similar procedure described in the
synthesis of 1 was adopted for the synthesis of 1A. Thiobenzoic
acid (0.280 g, 2 mmol) was used instead of thioacetic acid.
Elemental analysis of the residue after recrystallizing from chlo-
roform (0.388 g) was found to be in good agreement with the
formula Me2Sn(SOCPh)2. (91% yield) Mp: 143◦ C. Anal. Calcd
for SnC16H16O2S2: C, 45.42; H, 3.81; found: C, 45.40; H, 3.70.
References
1 R. Robson, Dalton Trans., 2008, 5113.
2 G. Fe´rey, Chem. Soc. Rev., 2008, 37, 191.
3 D. Maspoch, D. Ruiz-Molina and J. Vaciana, Chem. Soc. Rev., 2007,
36, 770.
4 A. K. Cheetham, C. N. R. Rao, and R. K. Feller, Chem. Commun.,
2006, 4780.
1H NMR (CDCl3, ppm): 1.19 (6H, Me), 7.4–8.09 (10 H, Ph) 13
C
5 C. Janiak, Dalton Trans., 2003, 2781.
NMR (CDCl3, ppm):4.6 (CH3), 128–137 (C6H5), 201.87 (COS).
119Sn NMR (CDCl3, Me4Sn, ppm): -76.66. IR (KBr pellet cm-1):
1628 n(CO), 1210 n(Ph–C), 929 n(C–S), 362 n( Sn–S).
6 P. Vaqueiro and M. Lucia Romero, Inorg. Chem., 2009, 48, 810.
7 S. Kitagawa, R. Kitaura and S. Noro, Angew. Chem., Int. Ed., 2004,
43, 2334.
8 J. R. Long and O. M. Yaghi, Chem. Soc. Rev., 2009, 38, 1213 and
references therein.
Attempted preparation of 1 using HCl [Synthesis of (Me2SnS)3
(4)]. A similar procedure described in the synthesis of 1 was
adopted. However, instead of InCl3, HCl (0.1 N, 0.1 mL) in
10 mL methanol was used. Elemental analysis of the residue after
recrystallizing from chloroform (0.321 g) was found to be in good
agreement with the molecular formula (Me2SnS)3. (59.2% yield)
Mp: 147 ◦C (reported: 148 ◦C). Anal. calcd for Sn3C6H18S3: C,
13.28; H, 3.34; found: 12.97; H, 3.22; 1H NMR (CDCl3, ppm) 0.8
(18H, Me). 13C NMR (CDCl3, ppm) 4.77. 119Sn NMR (CDCl3,
Me4Sn, ppm) 134.22.
9 D. J. Tranchemontagne, J. L. Mendoza-Corte´s, M. O’Keeffe and O. M.
Yaghi, Chem. Soc. Rev., 2009, 38, 1257.
10 H. Kajitani, H. Senio and Y. Mizobe, Organometallics, 2007, 26,
3499.
11 V. Jancik, Y. Peng, H. W. Roesky, J. Li, D. Neculai, A. M. Neculai and
R. Herbst-Irmer, J. Am. Chem. Soc., 2003, 125, 1452.
12 V. Jancik, H. W. Roesky, D. Neculai, A. M. Neculai and R. Herbst-
Irmer, Angew. Chem., Int. Ed., 2004, 43, 6192.
13 Z. Yang, X. Ma, Z. Zhang, H. W. Roesky, J. Magull and A. Ringe,
Z. Anorg. Allg. Chem., 2008, 634, 2740.
14 G. R. Clark, K. R. Flower, W. R. Roper and L. J. Wright,
Organometallics, 1993, 12, 3810.
15 N. Singh, S. Bhattacharya, H. No¨th and P. Mayer, Z. Naturforsch.,
2009, 64b, 1.
16 A. G. Davis, Organotin Chemistry, 2nd Ed.; Wiley VCH, GMBH, 1997,
p. 283.
NMR studies to explore reaction pathways
17 B. J. Aylett, Organometallic Compounds, part 2, group IV and V,
Chapman and Hall, John Wiley, New York, 1980, p. 234.
18 M. Saito, H. Hashimoto, T. Tajima and M. Ikeda, J. Organomet. Chem.,
2007, 692, 2729.
19 A. E. Reed and F. Weinhold, J. Chem. Phys., 1983, 78, 4066.
20 S. Bhattacharya, Spectrochim. Acta, Part A, 2005, 61, 3145.
21 D. L. Kepert, Prog. Inorg. Chem., 1977, 23, 1.
22 M. Rossi and F. Caruso;, J. Organomet. Chem., 2006, 691, 1535.
23 C. Ma, Y. Han, R. Zhang and D. Wang, Dalton Trans., 2004, 1832.
24 E. R. T. Tiekink, J. Organomet. Chem., 1991, 408, 323.
25 C. Vatsa, V. K. Jain, T. Kasavdas and E. R. T. Tiekink, J. Organomet.
Chem., 1991, 410, 135.
To 0.0010 g of dimethyltin oxide in an NMR tube a solution of
thioacetic acid (0.9 mL) in 0.5 mL CD3OD was added. 1H NMR
data was collected after 30 min. Two more spectra of the same
reaction mixture were recorded each with a gap of 1 h. A very
small quantity of anhydrous indium trichloride was then added to
the NMR tube and 1H NMR spectra were recorded after 15 min,
1 h and 4 h.
The same experiment was repeated using thiobenzoic acid in
place of thioacetic acid.
26 T. P. Lockhart, J. C. Calabrese and F. Devidson, Organometallics, 1987,
6, 2479.
27 X. Kong, T. B. Grindley, P. K. Bakshi and T. S. Cameron,
Organometallics, 1993, 12, 4881.
28 E. R. T. Tiekink, Appl. Organomet. Chem., 1991, 5, 1.
29 P. Singh, S. Bhattacharya, V. D. Gupta and H. No¨th, Chem. Ber., 1996,
129, 1093.
30 S. P. Narula, S. K. Bharadwaj, Y. Sharda, R. O. Day, L. Howe and
R. R. Holmes, Organometallics, 1992, 11, 2206.
31 A. D. Buckingham, Adv. Chem. Phys., 1967, 12, 107.
32 Y. Li, Z. R. Li, D. Wu, R. Y. Li, X. Y. Hao and C. C. Sun, J. Phys.
Chem. B, 2004, 108, 3145.
33 B. S. Furniss, A. J. Hannaford, P. W. G. Smith and A. R. Tatchell, Vogel’s
Textbook of Practical Organic chemistry, 5th edn, Dorling Kindersley,
India, 2006.
Conclusions
An organotin hydrosulfide compound, Me2Sn(SH)(O2CMe) (1)
was prepared by hydrolysing organotin thioacetate under con-
trolled conditions. Under similar mild hydrolytic conditions
the corresponding benzoate could not be isolated. Instead, the
thiobenzoate complex, Me2Sn(SOCPh)2 was obtained in excellent
yield indicating that there was no hydrolysis. The reaction mecha-
nisms could be explained on the basis of DFT calculations. X-ray
crystallography revealed a one dimensional polymeric structure of
Me2Sn(SH)(O2CMe). As a result of the polymeric structure the
compound showed an NLO response as well as semiconducting
behaviour (in the solid state) with a band gap of 1.01 eV.
34 A. Krishnan, S. K. Pal, T. Nandakumar, A. G. Samuelson and P. K.
Das, Chem. Phys., 2001, 265, 313.
35 P. C. Ray and P. K. Das, J. Phys. Chem., 1995, 99, 14414.
36 SAINT+, 6.02 ed., Bruker AXS, Madison, WI, 1999.
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 8018–8024 | 8023
©

View Article Online
37 G. M. Sheldrik, SHELX 97, Program for Crystal structure Refinement
from Diffraction Data, University of Gottingen, Gottingen, 1997.
38 L. J. Farrugia, J. Appl. Crystallogr., 1999, 32, 837.
39 C. T. Lee, W. T. Yang and R. G. Parr, Phys. Rev. B: Condens. Matter
Mater. Phys., 1988, 37, 785.
40 A. D. Becke, J. Chem. Phys., 1993, 98, 5648.
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E.
Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo,
R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi,
C. Pomelli, J. W. 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, Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford,
J. Cioslowski, B. B. Stefanov, J. B. 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. Gonzalez and J. A. Pople, Gaussian 03, Revision
D.01, Gaussian, Inc., Wallingford CT, 2004.
41 J. Tomasi, B. Mennucci and E. Cances, J. Mol. Struct. (Theochem),
1999, 464, 211.
42 B. Mennucci and J. Tomasi, J. Chem. Phys., 1997, 106, 5151.
43 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.
44 G. Schaftenaar and J. H. Noordik, Molden, J. Comput.-Aided Mol.
Des., 2000, 14, 123.
8024 | Dalton Trans., 2009, 8018–8024
This journal is
The Royal Society of Chemistry 2009
©