Synthesis of triphenyltin(IV) hydrosulfide

Article abstract of DOI:10.1016/j.ica.2010.12.014

Compounds of the type R₃SnSH are believed to be unstable (unless sterically protected by very bulky R groups) because of their facile condensation into the corresponding sulfide, (R₃Sn)₂S. One such compound, Ph₃SnSH has been synthesized by an one pot reaction of triphenyltin hydroxide with thiophosgene followed by the hydrolysis of the intermediate triphenyltin chlorothioformate. The product, triphenyltin hydrosulfide has been characterized by IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectral techniques. Single crystal X-ray analysis revealed that the molecule is a discrete monomer containing tin atom at the centre of a distorted tetrahedron. Plausible reaction mechanism for the formation of the molecule has also been reported.

Full text of DOI:10.1016/j.ica.2010.12.014

Inorganica Chimica Acta 367 (2011) 230–232
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Synthesis of triphenyltin(IV) hydrosulfide
⇑
Suryabhan Singh, Subrato Bhattacharya
Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221005, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 18 June 2010
Received in revised form 3 November 2010
Accepted 9 December 2010
Available online 16 December 2010
Compounds of the type R3SnSH are believed to be unstable (unless sterically protected by very bulky R
groups) because of their facile condensation into the corresponding sulfide, (R3Sn)2S. One such com-
pound, Ph3SnSH has been synthesized by an one pot reaction of triphenyltin hydroxide with thiophos-
gene followed by the hydrolysis of the intermediate triphenyltin chlorothioformate. The product,
triphenyltin hydrosulfide has been characterized by IR, 1H, 13C and 119Sn NMR spectral techniques. Single
crystal X-ray analysis revealed that the molecule is a discrete monomer containing tin atom at the centre
of a distorted tetrahedron. Plausible reaction mechanism for the formation of the molecule has also been
reported.
Keywords:
Organotin
Hydrosulfide
Tin sulfide
X-ray structure
119Sn NMR
Ó 2010 Elsevier B.V. All rights reserved.
Designing and synthesis of hydrosulfido complexes have at-
tracted a lot of attention over last two decades owing to their fas-
cinating structures, biological and catalytic properties [1–6].
Metal–sulfur bonding is of importance in bioinorganic [7–9] and
biomimetic chemistry [10–16] and the chemistry of SH-containing
complexes is of relevance to metal sulfide hydrosulfurization cata-
lysts [6,7]. Metal hydrosulfide complexes act as precursors for the
preparation of heterobimetallic complexes and clusters [17,18]. A
number of hydrosulfide complexes of transition metals are known
but analogous compounds of main group metals are scarce. The
main problem associated with the synthesis of hydrosulfide
complexes is their tendency to aggregated further leading to the
formation of di/polynuclear sulfide complexes and sometimes to
insoluble metal sulfides [1,19]. However, a few tin hydrosulfides
are known which have been stabilized by either steric protection
using highly bulky substituents or at a hypervalent tin centre
[19,20]. Very recently, we could isolate a hydrosulfidotin complex
in a rigid polymeric framework by controlled hydrolysis of a dior-
ganotin thiocarboxylate [21]. In spite of all these, compounds of
the type R3SnSH are believed to be non-isolable as they undergo
condensation reaction during their synthesis leading to formation
of organotin sulfides (R3SnSSnR3) [19,22]. Here, we report on a
novel method of synthesis of a triorganotin hydrosulfide without
incorporation of any appreciable steric protection which is ex-
pected to be a very useful precursor for bi/polynuclear complexes.
Our attempt to synthesize Ph3SnSH by passing H2S gas to a suspen-
sion of triphenyltin hydroxide was expectedly unsuccessful as the
product was bis-triphenyltin sulfide. Similarly, bubbling a stream
of H2S gas into a solution of triphenyltin chloride and triethyl-
amine also gave the same product due to facile condensation of
the desired hydrosulfide.
Though there is no thermochemical data available for such reac-
tions the Sn–S and S–H bonds are well known to be thermally sta-
ble [25]. However, the heat evolved during the formation of
R3SnSH is possibly enough to cross the energy barrier for the next
condensation step. If this presumption is true then any alternative
route which is endothermic (or less exothermic) should give the
hydrosulfide compound without its further condensation.
With this view, we tried to find out an entirely different route
[27]. Triphenyltin hydroxide in presence of triethylamine was trea-
ted with thiophosgene (CAUTION! Toxic) so that it formed triphen-
yltin chlorothionformate which then underwent a SNi reaction
forming the corresponding chlorothiolformate. The later was then
hydrolyzed leading to the formation of triphenyltin hydrosulfide
and chloroformic acid. Chloroformic acid being unstable decom-
posed into carbon dioxide and hydrochloric acid. As we have seen
earlier, in case of organotin thiocarboxylates hydrolysis may cleave
the Sn–S bond and S–C bond. However, acidic medium not only
facilitates cleavage of the S–C bond but also impedes formation
of another weak acid (H2S) and thus the condensation of the hydro-
sulfide groups to form organotin sulfide. The step wise mechanism
is shown in Scheme 1.
It is well known that
a reaction of H2S with organotin
compounds results into corresponding organotin sulfides [23,24].
An alternative mechanism may involve the slow hydrolysis of
thiophosgene [29] giving H2S, HCl and CO2 followed by the subse-
quent reaction of Ph3SnOH with H2S. The in situ generation of H2S
⇑
Corresponding author. Tel.: +91 542 2307321x107; fax: +91 542 2368127.
E-mail addresses: s_bhatt@bhu.ac.in, bhatt99@yahoo.com (S. Bhattacharya).
0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.12.014

S. Singh, S. Bhattacharya / Inorganica Chimica Acta 367 (2011) 230–232
231
In solution also the discrete molecular structure is retained as
evinced by presence of a 119Sn NMR peak at 81.43 ppm which is
indicative of a tetra-coordinated tin. The C–Sn–C bond angle in
solution could be estimated to be 108.9° from the 1J(119Sn–13C)
value [35].
Acknowledgments
The authors are grateful to Prof. Ram Lakhan, Banaras Hindu
University for useful discussion. Thanks are also due to Dr. A.K.
Shrivastava for providing a bottle of thiophosgene. Financial sup-
port from the council of scientific and industrial research, India is
also gratefully acknowledged.
Appendix A. Supplementary materials
CCDC 755649 contains the supplementary crystallographic data
forPh3SnSH. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/j.ica.
2010.12.014.
Scheme 1. Pluasible mechanism for the formation of Ph3SnSH.
may lead to the formation of Ph3SnSH very slowly thereby
lowering the chances of further condensation into triphenyltin sul-
fide. However, the formation of triphenyltin chlorothionformate
[Ph3SnOC(S)Cl] suggested in Scheme 1 are in accordance with
those reported for conversion of phenols to corresponding thiophe-
nols [30].
The molecular structure of Ph3SnSH is shown [31] in Fig. 1. The
geometry around Sn is approximately tetrahedral. The Sn1–S01
bond length 2.359(2) Å is slightly shorter than those in (Ph3Sn)2S
(2.397 Å) [34] and is comparable to that in Me2Sn(SH)(O2CMe)
[21]. Except SH. . .HC there is no other intermolecular contact of sig-
nificance. Intermolecular Sn–Sn and Sn–S distances are quite large
being 6.221 and 5.861 Å, respectively.
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Fig. 1. ORTEP view of Ph3SnSH.
81.43. IR (KBr): m(S–H) too weak to be observed [28].

232
[28]
S. Singh, S. Bhattacharya / Inorganica Chimica Acta 367 (2011) 230–232
m
(S–H) vibration in the IR spectra is observed as a weak band between 2500
structure were collected on a Bruker SMART APEX CCD diffractometer. The
structures were solved by direct methods (SHELXS-97) and then refined on F2 by
the full matrix least-squares technique with the SHELXL-97 software [32] using
WinGX program package [33].
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b = 9.732(4), c = 18.765(4), b = 105.644(4), V = 3328.4(13) Å3, Z = 7, F(0 0 0) =
1520, (Mo K
calcd = 1.529 mg mÀ3, k = 0.71073, T = 293 K, ) = 1.649 mmÀ1
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C18H16S1Sn1, monoclinic, space group P21/c, a = 19.018(4),
q
l
a
.