Hypercoordinated organotin compounds containing sulfur and chlorine. Molecular structures of [(Ph3P)2N]+[S(SnR2Cl) 2Cl]- (R=Me, t-Bu)

Article abstract of DOI:10.1016/S0022-328X(01)01069-5

The reaction of diorganotin sulfides, cyclo-(R₂SnS)_n (R=Me, n-Bu; n=3; R=t-Bu; n=2) with the corresponding diorganotin dichlorides, R₂SnCl₂, provided the tetraorganodistannathianes, (R₂ClSn)₂

Full text of DOI:10.1016/S0022-328X(01)01069-5

Journal of Organometallic Chemistry 636 (2001) 138–143
www.elsevier.com/locate/jorganchem
Hypercoordinated organotin compounds containing sulfur and
chlorine. Molecular structures of [(Ph3P)2N]+[S(SnR2Cl)2Cl]−
(R=Me, t-Bu)
Jens Beckmann a, Dainis Dakternieks a,*, Andrew Duthie a, Carissa Jones a,
Klaus Jurkschat b, Edward R.T. Tiekink c,d
a Centre for Chiral and Molecular Technologies, Deakin Uni6ersity, Geelong, Vic. 3217, Australia
b Fachbereich Chemie der Uni6ersita¨t Dortmund, Lehrstuhl fu¨r Anorganische Chemie II, 44221 Dortmund, Germany
c Department of Chemistry, The Uni6ersity of Adelaide, Adelaide 5005, Australia
d Department of Chemistry, National Uni6ersity of Singapore, Singapore 117543
Received 2 April 2001; accepted 4 June 2001
Dedicated to Professor Oleg Nefedov on the occasion of his 70th birthday
Abstract
The reaction of diorganotin sulfides, cyclo-(R2SnS)n (R=Me, n-Bu; n=3; R=t-Bu; n=2) with the corresponding diorganotin
1
dichlorides, R2SnCl2, provided the tetraorganodistannathianes, (R2ClSn)2S (1, R=Me; 2, R=n-Bu; 3, R=t-Bu). H-, 13C-, and
119Sn-NMR studies indicate that these compounds are kinetically labile and in equilibrium with the starting materials. Addition
of equimolar amounts of [(Ph3P)2N]Cl to the reaction mixtures gave the chloride complexes [(Ph3P)2N]+[S(SnR2Cl)2Cl]− (4,
R=Me; 5, R=n-Bu; 6, R=t-Bu). Single-crystal X-ray diffraction studies revealed the tin atoms in both 4 and 6 to adopt
distorted trigonal bipyramidal configurations with the chlorine atoms occupying the axial positions. © 2001 Elsevier Science B.V.
All rights reserved.
Keywords: Hypercoordination; Organotin; Dimeric tin sulfides
possessing two kinetically labile substituents
[2–4].
X
1. Introduction
Some 30 years ago, Davies and Harrison [5] de-
scribed the synthesis of analogous monomeric te-
traorganodistannathianes R2(X)SnSSn(X)R2 (X=F,
Cl, Br, I, SCN, OR, OOCR; R=alkyl) from the reac-
tion of diorganotin sulfides, R2SnS, with the appropri-
ate diorganotin species, R2SnX2. However, the reported
compounds were not well characterized at that time.
In the present work we briefly revisit the synthesis of
tetraorganodistannathianes R2(Cl)SnSSn(Cl)R2 (R=
Me, n-Bu, t-Bu) by the same method as reported by
Davies and Harrison [5] and provide evidence that in
some cases the products exist in equilibrium with the
starting compounds. Repeating the same reaction in the
presence of chloride ions gave rise to the formation of
anionic sulfur- as well as chloride-bridged ditin com-
plexes, namely [S(SnR2Cl)2Cl]− (R=Me, n-Bu, t-Bu),
which were isolated as their [(Ph3P)2N]+ salts.
Dimeric tetraorganodistannoxanes [R2(X)SnOSn(Y)-
R2]2 (X, Y=F, Cl, Br, OH, OR, OSiMe3, OOCR,
OSP(OR)2, NO3, N3, NCS, SH, OReO3; R=alkyl,
aryl) have received great interest as catalysts for a
variety of organic reactions. The catalytic activity has
been attributed to the kinetic lability in solution of the
ladder-like Sn4O2X2Y2 structural motif found in the
solid state [1]. Dimeric tetraorganodistannoxanes
[R2(X)SnOSn(X)R2]2 (X=Cl, Br, OAc; R=alkyl) are
easily accessible in high yields by reacting diorganotin
oxides, R2SnO, with diorganotin compounds, R2SnX2,
* Corresponding author. Fax: +61-3-5227-2218.
E-mail address: dainis@deakin.edu.au (D. Dakternieks).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01069-5

J. Beckmann et al. / Journal of Organometallic Chemistry 636 (2001) 138–143
139
2. Discussion
Bu2SnS)2 [8] and t-Bu2SnCl2 [6], respectively, while the
signal at 106.4 ppm is unambiguously assigned to the
Reacting diorganotin sulfides, cyclo-(R2SnS)n (R=
Me, n-Bu, t-Bu; n=2, 3), with the appropriate
amounts of diorganotin dichlorides, R2SnCl2 (R=Me,
n-Bu, t-Bu), in refluxing chloroform for 12 h resulted in
clear solutions [5]. From these solutions, the solvents
were allowed to evaporate slowly at room temperature
leaving colorless microcrystalline (R=Me (A), R=t-
Bu (C)) or waxy solids (R=n-Bu (B)). In contrast to
the work of Davies and Harrison, we found that none
of these solids gave sharp melting points but, instead,
melt over wide temperature ranges [5]. This suggests
that the solid materials A–C comprise a mixture of
different compounds, presumably the starting com-
pounds cyclo-(R2SnS)n (n=2, 3), and R2SnCl2 and/or
the tetraorganodistannathianes R2(Cl)SnSSn(Cl)R2
(R=Me (1), n-Bu (2), t-Bu (3)).
tetraorganodistannathiane
t-Bu2(Cl)SnSSn(Cl)t-Bu2
(3). The 13C-NMR spectrum (CDCl3) of material C
exhibits two sets of signals, each consisting of three
signals. The first set reveals signals belonging to the
quaternary carbon atoms of the tert-butyl groups at
45.1 (1J(13Cꢀ119Sn)=395 Hz), 42.7 (1J(13Cꢀ119Sn)=330
Hz), and 39.3 (1J(13Cꢀ119Sn)=360 Hz) which are as-
signed to t-Bu2SnCl2, t-Bu2(Cl)SnSSn(Cl)t-Bu2 (3), and
cyclo-(t-Bu2SnS)2, respectively. The second set shows
signals at 30.0, 29.8 and 29.2 ppm, which are related to
the methyl groups of the tert-butyl groups, however, no
additional assignment was made for these signals. The
1H-NMR spectrum (CDCl3) of the solid material C also
displays three equally intense signals at 1.44
(3J(1HꢀCCꢀ119/117Sn)=114 Hz), 1.41 (3J(1HꢀCCꢀ119
-
Sn)=108 Hz), and 1.39 ppm (3J(1HꢀCCꢀ119/117Sn)=90
Hz), which are assigned to t-Bu2SnCl2, t-Bu2(Cl)-
SnSSn(Cl)t-Bu2 (3), and cyclo-(t-Bu2SnS)2, respectively.
The 119Sn-NMR spectrum (CDCl3) of material A
shows a broad signal at 145.2 ppm revealing the pres-
ence of only one compound in solution, which is tenta-
tively assigned to Me2(Cl)SnSSn(Cl)Me2 (1). In contrast
to the dimeric structure of the corresponding te-
traorganodistannoxane, [Me2(Cl)SnOSn(Cl)Me2]2, the
119Sn chemical shift suggests the tin atoms of 1 to be
tetracoordinated. The 13C- and 1H-NMR spectra
1
The 119Sn-, 13C- and H-NMR results are in agreement
with an equilibrium between cyclo-(t-Bu2SnS)2, t-
Bu2SnCl2, and t-Bu2(Cl)SnSSn(Cl)t-Bu2 (3) being slow
on the NMR time scales.
In order to identify anionic organotin species associ-
ated with the aforementioned reactants in solution by
autodissociation, electrospray mass spectra of acetoni-
trile solutions of A, B and C were recorded in the
negative ion detection mode. In all cases the spectra
revealed two intense mass clusters with distinctive iso-
tope patterns related to the anions [R2SnCl3]− (254.9
for A, 338.9 for B, 338.9 for C) and [S(SnR2Cl)2Cl]−
(436.8 for A, 605.0 for B, 605.0 for C). The detection of
the latter anions supports the assignments made by
NMR spectroscopy, and confirms the presence of te-
traorganodistannathianes R2(Cl)SnSSn(Cl)R2 (R=Me
(1), n-Bu (2), t-Bu (3)) in solutions of the materials
A–C.
In summary, NMR spectroscopy and electrospray
mass spectrometry reveal the existence of tetraorgan-
odistannathianes in solutions of the materials A–C.
The wide melting point ranges are consistent with a
mixture of compounds in the solid state. Considering
the kinetically labile SnꢀCl and SnꢀS bonds, the most
likely explanation for this observation is the assump-
tion of equilibria between the starting materials and the
tetraorganodistannathianes (Scheme 1).
(CDCl3) of A show a signal at 6.8 ppm (1J(13Cꢀ119
-
Sn)=444 Hz) and 1.07 ppm (2J(1HꢀCꢀ119Sn)=66 Hz),
respectively.
For the material B, the 119Sn-NMR spectrum
(CDCl3) reveals two broad signals in the tetracoordi-
nated range at 136.5 (integral 85%) and 128.9 ppm
(integral 15%), which are close to the chemical shifts
reported for cyclo-(n-Bu2SnS)3 (l 126.9) [6] and n-
Bu2SnCl2 (l 123.4) [7]. This observation is consistent
with an equilibrium between cyclo-(n-Bu2SnS)3, n-
Bu2SnCl2, and n-Bu2(Cl)SnSSn(Cl)n-Bu2 (2). Consider-
ing the very similar 119Sn chemical shifts of the starting
materials, no unambiguous assignment of the signals
could be made. Apparently, the third signal is superim-
posed by one of the other broad signals. The 13C-NMR
spectrum (CDCl3) of B shows a very broad signal at
29.1 ppm, two broad signals at 27.4 and 26.3 ppm and
a reasonably sharp signal at 13.5 ppm. Consistent with
1
this, the H-NMR spectrum displays a broad signal at
1.73 ppm and two well-resolved multiplets at 1.37 and
0.92 ppm in an integral ratio of 4:2:3. The latter results
suggest the assumed equilibrium between cyclo-(n-
Bu2SnS)3, n-Bu2SnCl2, and n-Bu2(Cl)SnSSn(Cl)n-Bu2
Repeating the reaction of diorganotin sulfides, cyclo-
(R2SnS)n (R=Me, n-Bu, t-Bu; n=2, 3), with the ap-
propriate amounts of diorganotin dichlorides, R2SnCl2
(R=Me, n-Bu, t-Bu), in the presence of [(Ph3P)2N]Cl
produced [(Ph3P)2N]+[S(SnR2Cl)2Cl]− (R=Me (4), n-
Bu (5), t-Bu (6)) in almost quantitative yields (Scheme
1). Notably, the organotin anions of compounds 4–6
resemble the electrospray mass clusters mentioned
above. Compounds 4–6 represent colorless, sharp-melt-
1
(2) to be fast on the H- and 13C-NMR time scales.
The 119Sn-NMR spectrum (CDCl3) of the solid mate-
rial C shows three distinctive signals at 125.5 ppm
(2J(119SnꢀSꢀ117Sn)=117
Hz),
106.4
(2J(119Snꢀ
Sꢀ117Sn)=160 Hz) and 55.0 ppm in an integral ratio of
1:1:1. The signals at 125.5 and 55.0 ppm are undisput-
edly correlated to the starting compounds cyclo-(t-

140
J. Beckmann et al. / Journal of Organometallic Chemistry 636 (2001) 138–143
ing crystalline solids that are highly soluble in common
organic solvents.
to cyclo-(t-Bu2SnS)2, t-Bu2SnCl−3 , and [S(Snt-
Bu2Cl)2Cl]−, respectively. Notably, the position of the
signals associated with t-Bu2SnCl−3 and [S(Snt-
Bu2Cl)2Cl]− depend on the concentration of 6 in solu-
tion, however, no systematic studies were performed to
account for this concentration dependence. The 13C-
NMR spectrum (CDCl3) of 6 reveals two different sets
of resonances, each containing three signals, in the
range for alkyl carbon atoms. The signals related to the
quaternary carbon atoms are centered at 45.9
(1J(13Cꢀ119/117Sn)=674 Hz), 41.2 (1J(13Cꢀ119Sn)=459
Hz), and 38.9 ppm (1J(13Cꢀ119Sn)=356 Hz), and were
tentatively assigned to t-Bu2SnCl−3 , [S(Snt-Bu2Cl)2Cl]−,
and cyclo-(t-Bu2SnS)2, respectively. No assignment was
made for the signals at 30.5, 29.6 and 29.3 ppm as-
cribed to the methyl groups of the tert-butyl groups.
The 1H-NMR spectrum (CDCl3, low concentration)
shows three signals in the range of the alkyl protons at
1.46 (3J(1HꢀCCꢀ119Sn)=118 Hz, integral 45%), 1.43
(3J(1HꢀCCꢀ119Sn)=106 Hz, integral 10%), and 1.40
ppm (3J(1HꢀCCꢀ119Sn)=96 Hz, integral 45%), which
are unambiguously assigned to t-Bu2SnCl−3 , [S(Snt-
Bu2Cl)2Cl]−, and cyclo-(t-Bu2SnS)2, respectively. Con-
sequently, all NMR spectra of 6 are consistent with an
equilibrium between [S(Snt-Bu2Cl)2Cl]−, cyclo-(t-
Bu2SnS)2 and t-Bu2SnCl−3 in solution (Eq. (1)).
The 119Sn-NMR spectra (CDCl3) of 4 and 5 show
reasonably sharp signals in the range for pentacoordi-
nated tin atoms at −32.3 and −35.3 ppm, respec-
1
tively. The 13C- and H-NMR spectra (CDCl3) are also
consistent with the exclusive formation of 4 and 5 in
solution (Section 3).
The 119Sn-NMR spectrum (CDCl3) of 6 reveals a
sharp signal at 126.3 ppm (2J(119SnꢀSꢀ117Sn)=119 Hz,
integral 37%), a broad signal at −2.3 ppm (w1/2=200
Hz, integral 40%) and a very broad signal at −18.3
ppm (w1/2=400 Hz, integral 23%), which are assigned
Scheme 1.
(1)
2.1. Molecular structures of 4 and 6
Precise structural information for 4 and 6 were af-
forded by single-crystal X-ray diffraction studies. The
molecular structure of the anion in 4 is illustrated in
Fig. 1, that for 6 in Fig. 2 and selected geometric
parameters are collected in Table 1. The structures of 4
and 6 represent, as far as we are aware, the first
crystallographically examples containing a Sn(m-S)(m-
Cl)Sn core [9]. The anion in 4 is built up about a
parallelogram defined by the aforementioned ditin core
that has internal angles ranging from 82.50(5) to
100.22(7)°, with the most and least acute angles being
subtended at the bridging Cl(2) and S(1) atoms, respec-
tively. There is some disparity in the chloride bridge
Fig. 1. Molecular geometry for the anion in 4 showing the atomic
numbering scheme.
,
(DSnꢀCl(2) is 0.08 A) but the sulfide bridge is symmetri-
cal. The coordination sphere of each of the tin atoms is
completed by a terminal chlorine atom and two methyl
groups. The geometry about each tin atom is best
described as trigonal bipyramidal with the equatorial
and axial positions being occupied by two C and one S,
and by two Cl, respectively, in each case. The sum of
the trigonal angles is 359.1(3) and 358.4(2)°, respec-
tively, with the widest angle being subtended by the
methyl substituents. In this description the Sn(1) atom
Fig. 2. Molecular geometry for the anion in 6 showing the atomic
numbering scheme. Only one component of each of the disordered
C(11) and C(15) atoms is shown and hydrogen atoms have been
omitted for clarity.

J. Beckmann et al. / Journal of Organometallic Chemistry 636 (2001) 138–143
141
Table 1
ence is also reflected in the planarity of the atoms
comprising the core. Thus, in 6 the deviations of the
Sn(1), Sn(2), S(1) and Cl(2) atoms from their least-
squares plane are −0.0031(6), −0.0031(6), 0.088(3)
,
Selected bond lengths (A) and bond angles (°) for 4 and 6
a
4
6 b
,
Sn(1)ꢀS(1)
Sn(1)ꢀCl(1)
Sn(1)ꢀCl(2)
Sn(1)ꢀC(1)
Sn(1)ꢀC(x)
Sn(2)ꢀS(1)
Sn(2)ꢀCl(2)
Sn(2)ꢀCl(3)
Sn(2)ꢀC(y)
Sn(2)ꢀC(z)
N(1)ꢀP(1)
N(1)ꢀP(2)
2.399(2)
2.474(2)
2.744(2)
2.115(7)
2.134(9)
2.390(2)
2.828(2)
2.481(2)
2.110(7)
2.153(7)
1.590(5)
1.585(5)
2.380(2)
2.513(3)
2.743(3)
2.17(1)
2.179(10)
2.388(3)
2.755(2)
2.482(2)
2.18(1)
and 0.062(3) A, respectively. This contrasts the respec-
tive deviations of the atoms from the comparable plane
,
in 4, i.e. 0.0040(2), 0.0468(6), −0.476(2), −0.390(2) A,
indicating significant buckling. It would appear that
this difference between the structures can be related to
the substitution of the methyl groups in 4 by the
tert-butyl groups in 6.
An examination of the Sn-donor atom parameters
listed in Table 1 reveals some interesting variations.
The Sn(1)ꢀCl(2) distances are equivalent in 4 and 6 but,
Sn(1)ꢀS(1) and Sn(1)ꢀCl(1) are significantly shorter and
longer, respectively, in 6. Both pairs of Sn(2)ꢀS(1) and
Sn(2)ꢀCl(3) distances are experimentally equivalent in 4
and 6 but, Sn(2)ꢀCl(2) is significantly shorter in 6. A
consistent observation is that the magnitude of the
SnꢀC bond distances are increased in 6 compared with
4. With the exception of the narrowing of the CꢀSnꢀC
angles (by ca. 5°) in 6 compared with those in 4, the
majority of angles subtended at the tin atoms involving
a carbon atom in 6 are either equivalent (one case) or
significantly wider. Notably, this has the result that the
SꢀSnꢀCl and ClꢀSnꢀCl angles are uniformly more acute
in 6. The reduction in these latter angles is accompa-
nied by an expansion of the Sn(1)ꢀS(1)ꢀSn(2) and
Sn(1)ꢀCl(2)ꢀSn(1) angles and hence, a reduction of
steric strain at the bridging atoms.
2.19(1)
1.558(7)
1.539(7)
S(1)ꢀSn(1)ꢀCl(1)
S(1)ꢀSn(1)ꢀCl(2)
S(1)ꢀSn(1)ꢀC(1)
S(1)ꢀSn(1)ꢀC(x)
Cl(1)ꢀSn(1)ꢀCl(2)
Cl(1)ꢀSn(1)ꢀC(1)
Cl(1)ꢀSn(1)ꢀC(x)
Cl(2)ꢀSn(1)ꢀC(1)
Cl(2)ꢀSn(1)ꢀC(x)
C(1)ꢀSn(1)ꢀC(x)
S(1)ꢀSn(2)ꢀCl(2)
S(1)ꢀSn(2)ꢀCl(3)
S(1)ꢀSn(2)ꢀC(y)
S(1)ꢀSn(2)ꢀC(z)
Cl(2)ꢀSn(2)ꢀCl(3)
Cl(2)ꢀSn(2)ꢀC(y)
Cl(2)ꢀSn(2)ꢀC(z)
C(y)ꢀSnꢀC(z)
89.41(6)
85.65(6)
117.8(2)
117.0(3)
175.06(6)
95.8(2)
93.7(3)
86.7(2)
88.4(3)
124.3(4)
83.98(6)
90.64(6)
116.8(2)
116.6(2)
173.63(6)
89.7(2)
85.12(8)
81.44(8)
122.5(4)
119.0(3)
166.55(8)
96.9(3)
93.3(3)
90.0(3)
93.6(3)
118.2(4)
81.04(7)
84.60(9)
119.6(4)
120.5(3)
165.64(9)
92.4(3)
83.6(2)
91.2(3)
125.0(3)
100.22(7)
82.50(5)
134.3(3)
119.6(5)
108.11(9)
89.18(7)
145.0(5)
Sn(1)ꢀS(1)ꢀSn(2)
Sn(1)ꢀCl(2)ꢀSn(2)
P(1)ꢀN(1)ꢀP(2)
The 119Sn-MASNMR spectrum of 6 reveals two sig-
nals at −75.8 and −82.5 ppm, and is therefore fully
consistent with the number of crystallographically inde-
pendent tin sites in the molecular structure. The closest
non-hydrogen (and non-disordered component) contact
in the lattice occurs between the C(7) and C(32)ii atoms,
a x=2, y=3, z=4.
b x=5, y=9, z=13.
,
lies 0.1172(2) A above the trigonal plane in the direc-
tion of the Cl(2) atom; the Sn(2) atom lies 0.1606(6) A
above its C2S plane towards the Cl(3) atom. The re-
spective ClꢀSnꢀCl axial angles are 175.06(6) and
173.63(6)°. As expected, the SnꢀCl(bridging) distances
are significantly longer than the SnꢀCl(terminal) dis-
,
i.e. between anion and cation, at 3.51(2) A; symmetry
operation ii: x, 1−y, 3/2−z.
,
3. Experimental
tance. The closest contact in the lattice occurs between
the ions such that Cl(1)···H(29) is 2.66 A; symmetry
All manipulations with air sensitive compounds were
carried out under Ar using standard vacuum line and
Schlenk techniques. Reagent grade solvents were dried
over the appropriate desiccants and freshly distilled
prior to use. cyclo-(Me2SnS)3, cyclo-(n-Bu2SnS)3, [11]
cyclo-(t-Bu2SnS)2, [8] and t-Bu2SnCl2 [12] were pre-
pared according to literature procedures. Me2SnCl2,
n-Bu2SnCl2, and [(Ph3P)2N]Cl were obtained from
Fluka and Aldrich. NMR spectra were recorded using
i
,
operation i: 2−x, 1/2+y, −z. The geometry of the
[(Ph3)2PN]+ cation is as expected [10]. The structure of
the anion in 6 is in essential agreement with that found
in 4 but with some notable differences.
The range of angles within the Sn(m-S)(m-Cl)Sn core
is significantly greater in 6, i.e. 81.04(7)–108.11(9)° and
attendant with this is the observation that both chloride
and sulfide bridges are symmetric. Clearly, there is a
significant relief of steric strain within the Sn(m-S)(m-
Cl)Sn core in 6 compared with that in 4 so that the
angles subtended at the bridging S(1) and Cl(2) have
increased by about 8 and 7°, respectively. This differ-
1
a Varian 300 MHz Unity Plus NMR spectrometer. H,
13C, 31P and 119Sn chemical shifts (l) are given in ppm
and are referenced against Me4Si, H3PO4, and Me4Sn.
Electrospray mass spectra were obtained with a Plat-
form II single quadrupole mass spectrometer (Micro-

142
J. Beckmann et al. / Journal of Organometallic Chemistry 636 (2001) 138–143
mass, Altrincham, UK) using an MeCN mobile phase.
Acetonitrile solutions (0.1 mM) of the compounds
were injected directly into the spectrometer via a
Rheodyne injector equipped with a 50 ml loop. A
Harvard 22 syringe pump delivered the solutions to
the vaporization nozzle of the electrospray ion source
at a flow rate of 10 ml min−1. Nitrogen was used as
both a drying gas and for nebulization with flow rates
of ca. 200 and 20 ml min−1, respectively. Pressure in
the mass analyzer region was usually about 4×10−5
mbar. Typically ten signal-averaged spectra were col-
lected. Microanalyses were performed by CMAS, Bel-
mont, Australia.
(1J(13Cꢀ119Sn)=535 Hz), 27.8 (2J(13CꢀCꢀ119/117Sn)=
34 Hz), 26.2 (3J(13CꢀCCꢀ119/117Sn)=102 Hz), 13.6.
31P-NMR (CDCl3): l=21.2. 119Sn-NMR (CDCl3):
l= −35.3. Anal. Found. C, 55.4; H, 6.3; Cl, 9.6; N,
1.2. Calc. for C52H66Cl3NP2SSn2 (1143.0): C, 54.7; H,
5.8; Cl, 9.3; N, 1.2%.
[(Ph3P)2N]+[S(Snt-Bu2Cl)2Cl]− (6) (1052 mg, 92%,
m.p. 193–194 °C). 1H-NMR (CDCl3): l=1.46
(3J(1HꢀCCꢀ119Sn)=118 Hz, integral 45%; t-Bu2SnCl−3
), 1.43 (3J(1HꢀCCꢀ119Sn)=106 Hz, integral 10%; 6),
1.40 (3J(1HꢀCCꢀ119Sn)=96 Hz, integral 45%; cyclo-(t-
1
Bu2SnS)2). H-NMR (CDCl3): l=133.7, 131.8, 129.4,
126.6 (PPN), 45.9 (1J(13Cꢀ119/117Sn)=674 Hz; CMe3,
t-Bu2SnCl−3 ), 41.2 (1J(13Cꢀ119Sn)=459 Hz; CMe3, 6),
38.9 (1J(13Cꢀ119Sn)=356 Hz; CMe3, cyclo-(t-
Bu2SnS)2), 30.5, 29.6, 29.3 (CMe3). 31P-NMR (CDCl3):
l=21.1. 119Sn-NMR (CDCl3): l=126.3 (2J(119Snꢀ
Sꢀ117Sn)=119 Hz, integral 37%; cyclo-(t-Bu2SnS)2),
−2.3 (integral 40%, t-Bu2SnCl−3 ), −18.3 (integral
23%, 6). 119Sn-MAS NMR: l= −75.8, −82.5. Anal.
Found. C, 54.8; H, 6.0; Cl, 9.3; N, 1.2. Calc. for
C52H66Cl3NP2SSn2 (1143.0): C, 54.7; H, 5.8; Cl, 9.3; N,
1.2%.
3.1. Reactions between cyclo-(R2SnS)n and R2SnCl2
(R=Me, n-Bu, t-Bu; n=2, 3)
A mixture of cyclo-(R2SnS)n (181 mg, 0.33 mmol for
R=Me, n=3; 265 mg, 0.33 mmol for R=n-Bu, n=
3, 265 g, 0.50 mmol for R=t-Bu, n=2) and R2SnCl2
(219 mg, 1.00 mmol for Me; 304 mg, 1.00 mmol for
R=n-Bu; 304 g, 1.00 mmol for R=t-Bu) in CHCl3 (3
ml) was heated at reflux for 12 h. The solvent was
allowed to evaporate slowly to give microcystalline or
waxy solid materials, designated as A (R=Me, m.p.
55–164 °C), B (R=n-Bu, m.p. 36–44 °C), and C
(R=t-Bu, m.p. 61–145 °C). 119Sn-, 13C- and 1H-
NMR spectra were discussed in the text.
3.3. Crystallography
Intensity data for colorless 4 and 6 were measured
on a Rigaku AFC7R (AFC6R for 6) diffractometer at
173 K (293 K for 6) employing Mo–Ka radiation and
the ꢀ:2q scan technique such that qmax was 27.5°
(27.9°). Corrections were made for Lorentz and polar-
ization effects [13] and for absorption employing an
empirical procedure [14]. Crystallographic data are
summarized in Table 2.
3.2. Synthesis of [(Ph3P)2N]+[S(SnR2Cl)2Cl]− (R=Me
(4), n-Bu (5), t-Bu (6))
A mixture of cyclo-(R2SnS)n (181 g, 0.33 mmol for
R=Me, n=3; 265 g, 0.33 mmol for R=n-Bu, n=3;
265 g, 0.50 mmol for R=t-Bu, n=2), R2SnCl2 (219
mg, 1.00 mmol for Me; 304 mg, 1.00 mmol for R=n-
Bu; 304 g, 1.00 mmol for R=t-Bu), and [(Ph3P)2N]Cl
(574 mg, 1.00 mmol) in CHCl3 (3 ml) was heated at
reflux for 12 h. The solvent was removed in vacuo to
give colorless crystalline materials, which were recrys-
tallized from hexane–CH2Cl2.
Each structure was solved by heavy-atom methods
[15] and refined by a full-matrix least-squares proce-
dure based on F [13]. For 4, non-hydrogen atoms were
refined with anisotropic displacement parameters and
hydrogen atoms were included in the model at their
calculated positions. An analogous strategy was em-
ployed in the refinement of 6 with the following excep-
tion. Significant thermal motion was noted for the
methyl groups and for two of these, i.e. the C(11) and
C(15) atoms, two distinct positions were discerned.
From isotropic refinement, these were ascribed 50%
site occupancy factors; hydrogen atoms were not in-
cluded for the disordered groups. After the inclusion
of a weighting scheme of the form w=1/[|2(F)+
[(Ph3P)2N]+[S(SnMe2Cl)2Cl]− (4) (926 mg, 95%,
1
m.p. 194–195 °C). H-NMR (CDCl3): l=7.7–7.4 (m,
1
30H; Ph), 1.14 (s, 12H, J(1Hꢀ119/117Sn)=76 Hz; Me).
13C-NMR (CDCl3): l=133.7, 131.8, 129.4, 126.6
(phenyl carbons), 13.0 (1J(13Cꢀ119Sn)=573 Hz; Me).
31P-NMR (CDCl3): l=21.2. 119Sn-NMR (CDCl3):
d= −34.3. Anal. Found. C, 49.2; H, 4.2; Cl, 10.9; N,
1.3. Calc. for C40H42Cl3NP2SSn2 (974.6): C, 49.3; H,
4.3; N, 1.4; Cl, 10.9%.
2
gꢀFꢀ ], the refinements were continued until conver-
[(Ph3P)2N]+[S(Snn-Bu2Cl)2Cl]− (5) (982 mg, 86%,
m.p. 97–99 °C). 1H-NMR (CDCl3): l=7.7–7.4 (m,
30H; Ph), 1.83 (tt, 8H; SnCH2CH2), 1.67 (t, 8H,
2J(1HꢀCꢀ119/117Sn)=72 Hz; SnCH2), 1.38 (tq, 8H;
CH2CH3), 0.88 (t, 12H; CH2CH3). 13C-NMR (CDCl3):
l=133.7, 131.8, 129.4, 126.6 (phenyl carbons), 31.4
gence. The absolute structure of 4 was determined
based on differences in the refinements for the opposite
hands. Final refinement details are given in Table 2
and the crystallographic numbering schemes are shown
in Figs. 1 and 2 which were drawn at the 50% proba-
bility level [16].

J. Beckmann et al. / Journal of Organometallic Chemistry 636 (2001) 138–143
143
Table 2
Crystallographic data and structural parameters for 4 and 6
Acknowledgements
The Australian Research Council is thanked for sup-
port of the crystallographic facility. We are grateful to
Dr James M. Hook (University of New South Wales,
Sydney, Australia) for recording the 119Sn-MAS NMR
spectrum of 6.
Compound
4
C
974.5
0.11×0.21×0.57
Monoclinic
P21
6
Empirical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
40H42Cl3NP2SSn2 C52H66Cl3NP2SSn2
1142.9
0.07×0.11×0.36
Monoclinic
C2/c
Unit cell dimensions
,
a (A)
10.886(4)
12.662(6)
14.925(3)
92.63(2)
2055(1)
2
1.575
972
15.68
5196
4946
3799, n=3
0.028
0.004
0.028
39.75(1)
14.872(4)
19.983(6)
112.39(3)
10921(6)
8
1.390
4656
11.91
11564
11372
4722, n=2
0.054
0.00001
0.040
0.64
,
b (A)
References
,
c (A)
i (°)
V (A )
[1] J. Beckmann, K. Jurkschat, U. Kaltenbrunner, S. Rabe, M.
Schu¨rmann, D. Dakternieks, A. Duthie, D. Mu¨ller,
Organometallics 19 (2000) 4887 (and references cited therein).
[2] A.G. Davies, P.G. Harrison, P.R. Palan, J. Chem. Soc. C (1970)
2030.
[3] D. Dakternieks, K. Jurkschat, S. van Dreumel, E.R.T. Tiekink,
Inorg. Chem. 36 (1997) 2023.
[4] J. Beckmann, K. Jurkschat, S. Rabe, M. Schu¨rmann, D. Dak-
ternieks, Z. Anorg. Allg. Chem. 627 (2001) 458.
[5] A.G. Davies, P.G. Harrison, J. Chem. Soc. C (1970) 2035.
[6] B. Wrackmeyer, Annu. Rep. NMR Spectrosc. 16 (1985) 73.
[7] P.J. Smith, L. Smith, Inorg. Chim. Acta Rev. 7 (1973) 11.
[8] H. Puff, G. Bertram, B. Ebeling, M. Franken, R. Gattermayer,
R. Hundt, W. Schuh, R. Zimmer, J. Organomet. Chem. 379
(1989) 235.
3
,
Z
Dcalc (cm−3
F(000)
)
v (cm−1
)
Measured data
Unique data
Data with I]n|(I)
R
g
Rw
−3
,
z (e A
)
0.39
[9] G.R. Lewis, I. Dance, J. Chem. Soc. Dalton Trans. (2000) 299.
[10] F.H. Allen, O. Kennard, Chem. Des. Automat. News (1993) 8.
[11] H. Schumann, Z. Anorg. Allg. Chem. 354 (1967) 192.
[12] A.L. Allred, S.A. Kandil, J. Chem. Soc. A (1970) 2987.
[13] TEXSAN, Structure Analysis Package, Molecular Structure Cor-
poration, TX, 1992.
[14] N. Walker, D. Stuart, Acta Crystallogr. Sect. A 39 (1983) 158.
[15] P.T. Beurskens, G. Admiraal, G. Beurskens, W.P. Bosman, S.
Garc´ıa-Granda, J.M.M. Smits, C. Smykalla, The DIRDIF Pro-
gram System, Technical Report of the Crystallography Labora-
tory, University of Nijmegen, The Netherlands, 1994.
[16] C.K. Johnson, ORTEP-II, Report ORNL-5138, Oak Ridge Na-
tional Laboratory, Oak Ridge, TN, 1976.
4. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 160108 and 157770 for com-
pounds 4 and 6, respectively. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(Fax: +44-1223-336033; e-mail: deposit@ccdc.cam.
ac.uk or www: http://www.ccdc.cam.ac.uk).