Silicon-lead chalcogenides of the types Me4Si2(E)2PbPh2 and Ph2Pb(E)2Si2Me2 (E)2PbPh2 (E = S, Se) and related compounds containing tin and antimony

Article abstract of DOI:10.1016/S0022-328X(01)01450-4

The reaction of a 1:1 mixture of Ph₂PbCl ₂ and ClSiMe₂-SiMe₂Cl with H₂S/NEt₃ yielded the mixed silicon-lead sulfide Me₄Si₂(S)₂PbPh₂ (1a), a bicyclic silicon lead sulfide, Ph₂Pb(S) ₂Si₂Me₂(S)₂PbPh₂ (1b) was obtained by similar treatment of a 2:1 mixture of Ph₂ PbCl₂ and Cl₂SiMe-SiMeCl₂. The corresponding selenium compounds (2a-b) were obtained by reactions of mixtures of Ph₂PbCl₂ and methylchlorodisilanes with Li₂Se in THF. All products were characterized by multinuclear (¹H, ¹³C, ²⁹Si, ⁷⁷Se and ²⁰⁷Pb) NMR spectroscopy. The molecular structure of 1a is reported revealing a central five membered ring Si₂S₂Pb in envelope conformation with one sulfur atom (S1) above the plane defined by the atoms Pb1-S2-Si2-Si1. For comparison, the tin compounds Me₄Si₂(Se) ₂SnPh₂ (4a), and Ph₂Sn(Se) ₂Si₂Me₂(Se)₂SnPh₂ (4b) have also been prepared essentially applying the same procedure as for compounds 2a-b. A plot of δ (²⁰⁷Pb) of 1a-2b versus δ (¹¹⁹Sn) of the corresponding tin compounds 3a-4b exhibits a linear correlation with a slope of 4.11 (±0.17). Attempts to build related cycles containing a Group 15 element led to the isolation of the antimony compounds Me₄Si₂ (E)₂SbPh (5a: E = S, 5b: E = Se) starting from ClSiMe₂-SiMe₂-SiMe₂Cl, PhSbCl₂ and either H₂S/NEt₃ or Li₂Se.

Full text of DOI:10.1016/S0022-328X(01)01450-4

Journal of Organometallic Chemistry 648 (2002) 220–225
www.elsevier.com/locate/jorganchem
Silicon-lead chalcogenides of the types Me Si (E) PbPh and
4
2
2
2
Ph Pb(E) Si Me (E) PbPh (E=S, Se) and related compounds
2
2
2
2
2
2
containing tin and antimony
a,
b
Uwe Herzog *, Gerd Rheinwald
a
Institut f u¨ r Anorganische Chemie, TU Bergakademie Freiberg, Leipziger Straße 29, D-09596 Freiberg, Germany
b
Institut f u¨ r Chemie, Lehrstuhl Anorganische Chemie, TU Chemnitz, Straße der Nationen 62, D-09111 Chemnitz, Germany
Received 3 September 2001; received in revised form 29 October 2001; accepted 29 October 2001
Abstract
The reaction of a 1:1 mixture of Ph PbCl2 and ClSiMe –SiMe Cl with H S/NEt yielded the mixed silicon–lead sulfide
2
2
2
2
3
Me Si (S) PbPh (1a), a bicyclic silicon lead sulfide, Ph Pb(S) Si Me (S) PbPh (1b) was obtained by similar treatment of a 2:1
4
2
2
2
2
2
2
2
2
2
mixture of Ph PbCl2 and Cl SiMe–SiMeCl . The corresponding selenium compounds (2a–b) were obtained by reactions of
2
2
2
1
13
mixtures of Ph PbCl and methylchlorodisilanes with Li Se in THF. All products were characterized by multinuclear ( H, C,
2
207
2
2
29
77
Si, Se and Pb) NMR spectroscopy. The molecular structure of 1a is reported revealing a central five membered ring Si S Pb
2
2
in envelope conformation with one sulfur atom (S1) above the plane defined by the atoms Pb1ꢀS2ꢀSi2ꢀSi1. For comparison, the
tin compounds Me Si (Se) SnPh (4a), and Ph Sn(Se) Si Me (Se) SnPh (4b) have also been prepared essentially applying the
4
2
2
2
2
2
07
2
2
2
2
2
119
same procedure as for compounds 2a–b. A plot of l ( Pb) of 1a–2b versus l ( Sn) of the corresponding tin compounds 3a–4b
exhibits a linear correlation with a slope of 4.11 (90.17). Attempts to build related cycles containing a Group 15 element led to
the isolation of the antimony compounds Me Si (E) SbPh (5a: E=S, 5b: E=Se) starting from ClSiMe –SiMe Cl, PhSbCl and
4
2
2
2
2
2
either H S/NEt or Li Se. © 2002 Elsevier Science B.V. All rights reserved.
2
3
2
Keywords: NMR spectroscopy; Silicon–lead chalcogenides; Antimony; Tin
1. Introduction
Recently we have reported on the synthesis of cyclic
and bicyclic chalcogenides of the types Me Si (E) MR
4
2
2
x
(
E=S, Se, Te, MR =BPh, C(CH ) , SiMe , SiMePh,
x 2 5 2
(2)
SiPh , GeMe , SnMe ) [1] and R M(E) Si Me (E) MR
(
GeMe , SnMe ) [2]. For M=B, Si, Ge and Sn these
compounds have been prepared by reacting a mixture
of the corresponding dichloride and either ClSiMe2–
SiMe Cl or Cl SiMe–SiMeCl with lithium sulfide, sele-
2
2
2
2
2
2
2
2
2
In absence of the methylchlorodisilanes the diorgan-
odichlorides of Group 14 elements (Si, Ge, Sn) react
with lithium or sodium chalcogenides under formation
E=S, Se, Te, MR =C(CH ) , SiMe , SiMePh, SiPh ,
2 2 5 2 2
2
2
of trimeric diorganochalcogenides (R
ME) [1,3,4].
2
3
A related lead sulfide, (Ph PbS) , was described for
2
2
2
2
3
nide or telluride Eqs. (1) and (2):
the first time in 1887 [5]. Crystal structure analysis of
cis–trans-(PhMeSiS) [6], (Me SnS) [7,8], (Me SnSe)
3
2
3
2
3
[
(
9], (Me SnTe)3 [10], (Ph SnS)3 [11], (Ph PbS)3 [11],
o-Tol PbS) [12] and (p-Tol PbS) [12] have been re-
2 3 2 3
2 2 2
(
1)
ported revealing non-planar six-membered rings M E
3
3
which adopt a twisted boat conformation.
On the other hand, ClSiMe –SiMe Cl reacts with
2
2
*
Corresponding author. Tel.: +49-3731-394343; fax: +49-3731-
94058.
E-mail address: uwe.herzog@chemie.tu-freiburg.de (U. Herzog).
Li E (E=S, Se, Te) under formation of the six mem-
3
0
2
bered ring compounds E(SiMe –SiMe ) E. Molecular
2
2 2
022-328X/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01450-4

U. Herzog, G. Rheinwald / Journal of Organometallic Chemistry 648 (2002) 220–225
221
structure analyses for E=S and Se have shown that in
these cases the six-membered rings adopt chair confor-
mations [1].
pound Me Sn (Se) SnMe [14]. While in the first case
4 2 2 2
the five-membered rings adopt twist conformations
(very similar to the calculated geometry of
Me Si (S) SiMe [13]) the latter shows an envelope con-
DFT calculations on the system (Eq. (3)):
4
2
2
2
formation with the distannane unit and the two sele-
nium atoms in one plane.
The aim of this work is to extend these investigations
on five membered rings containing a disilane unit as
well as another Group 14 element linked by chalcogen
atoms towards lead containing cyclic and bicyclic
chalcogenides.
(
3)
revealed that the formation of the five membered ring
compound is accompanied by a decrease in the total
−
1
energy of 36 kJ mol
in accordance with the observed
favorite formation of these five membered rings [13]. So
far, molecular structures of such unfused five-mem-
bered rings are only known for the dimeric compound
Me Si (S) SiMe–SiMe(S) Si Me [1] and the tin com-
2
. Results and discussion
A 1:1 molar mixture of diphenyldichloroplumbane,
4
2
2
2
2
4
prepared by treatment of a suspension of Ph Pb in
4
CHCl with HCl, and 1,2-dichlorotetramethyldisilane
3
yielded on treatment with either H S–NEt or Li Se the
2
3
2
new compounds 1a and 2a containing a five membered
ring Si E Pb (see Scheme 1). The corresponding bicyclic
2
2
compounds 1b and 2b were observed by similar reac-
tions of a 2:1 molar mixture of Ph PbCl and 1,1,2,2-te-
2
2
trachlorodimethyldisilane (Scheme 1).
The NMR data of 1a–2b are summarized in Table 1.
So far the NMR data of the corresponding tin com-
pounds have only been known for E=S (3a–b [1,2],
for E=Se similar compounds with SnMe units instead
2
of SnPh have been reported, too in [1,2]). Therefore,
2
the tin compounds 4a and 4b have also been prepared
applying essentially the same procedure as for the lead
compounds 2a–b, the NMR data of 3a–4b are given in
Table 2.
29
While the Si-NMR chemical shifts of the lead con-
taining cycles and bicycles are close to those of the
Scheme 1.
Table 1
NMR data of silicon–lead heterocycles (chemical shifts in ppm, coupling constants in Hz)

222
U. Herzog, G. Rheinwald / Journal of Organometallic Chemistry 648 (2002) 220–225
Table 2
been observed before for lSi and lSn in corresponding
silicon and tin compounds [1].
The molecular structure analysis of 1a (Fig. 2) re-
NMR data of silicon–tin and silicon–antimony heterocycles
Me Si (E)SnPh and Ph Sn(E) Si Me (E) SnPh (E=S, Se (3a–4b)
4
2
2
2
2
2
2
2
2
and Me Si (E) SbPh (5a–b); chemical shifts in ppm, coupling con-
stants in Hz)
4
2
2
vealed a central five membered ring PbS Si that adopts
2
2
an envelope conformation. The interplanar angle be-
tween the planes formed by Pb(1)ꢀS(2)ꢀSi(2)ꢀSi(1) and
Pb(1)ꢀS(1)ꢀSi(1) is 41.65(3)°. The sulfur atom S(1) is
1
.032(1) A out of the plane defined by the atoms
,
Pb(1)ꢀS(2)ꢀSi(2)ꢀSi(1). This may also be the reason for
the difference in the angles Pb(1)ꢀS(1)ꢀSi(1) and
Pb(1)ꢀS(2)ꢀSi(2) of almost 5°, see Table 3. The bond
lengths PbꢀS and PbꢀC are comparable with the values
found in the molecular structure of (Ph PbS) (average
2
3
PbꢀS: 2.491 A, PbꢀC: 2.191 A [11]). Due to the smaller
, ,
ring size the angles SꢀPbꢀS as well as those at the sulfur
atoms are smaller than in (Ph PbS) (average SꢀPbꢀS:
2
3
1
09.4°, PbꢀSꢀPb: 104.4°).
Fig. 2. ORTEP plot of the molecular structure of 1a.
Fig. 1. 207Pb- vs. 119Sn-NMR chemical shifts in Me Si (E) MPh and
4
2
2
2
Table 3
Selected bond distances (A) bond angles and dihedral angles (°) of 1a
,
Ph M(E) Si Me (E) MPh (M=Sn, Pb; E=S, Se; 1a–4b).
2
2
2
2
2
2
Atoms
Distances
Atoms
Angles
7
7
corresponding tin containing derivatives, the Se-NMR
chemical shifts of 2a–b are 77 and 64 ppm, respectively,
at lower field than those of 4a–b. It has been stated
Si(1)ꢀSi(2)
Si(1)ꢀS(1)
Si(2)ꢀS(2)
Pb(1)ꢀS(1)
Pb(1)ꢀS(2)
Pb(1)ꢀC(1)
Pb(1)ꢀC(7)
Si(1)ꢀC(13)
Si(1)ꢀC(14)
Si(2)ꢀC(15)
Si(2)ꢀC(16)
2.356(2)
2.151(2)
2.140(2)
2.4995(11)
2.4915(11)
2.197(3)
2.204(4)
1.868(4)
1.870(5)
1.877(5)
1.859(5)
S(1)ꢀPb(1)ꢀS(2)
Pb(1)ꢀS(1)ꢀSi(1)
Pb(1)ꢀS(2)ꢀSi(2)
S(1)ꢀSi(1)ꢀSi(2)
S(2)ꢀSi(2)ꢀSi(1)
C(1)ꢀPb(1)ꢀC(7)
C(13)ꢀSi(1)ꢀC(14)
C(15)ꢀSi(2)ꢀC(16)
Pb(1)ꢀS(2)ꢀSi(2)ꢀSi(1)
S(1)ꢀPb(1)ꢀS(2)ꢀSi(2)
Si(1)ꢀS(1)ꢀPb(1)ꢀS(2)
Si(2)ꢀSi(1)ꢀS(1)ꢀPb(1)
S(2)ꢀSi(2)ꢀSi(1)ꢀS(1)
103.96(4)
95.73(5)
2
07
100.48(5)
108.63(6)
111.17(6)
120.51(13)
110.2(2)
109.7(3)
−3.28(8)
27.73(6)
before [15] that in many compounds the
Pb-NMR
Sn-NMR data of the
analogous tin compounds by a factor of ca. 3.0. A
119
chemical shifts parallel the
2
07
119
correlation of the
Pb- and
Sn-NMR chemical
shifts of 1a–4b is given in Fig. 1, but the slope of the
linear fit is with 4.11 somewhat larger. Compared with
the six membered ring trimeric diphenyllead sulfide,
Ph PbS) (l : 173.4 ppm [11]), the Pb-NMR signals
of the five membered ring compounds 1a–b are shifted
by more than 70 ppm to lower field. This trend has
−42.39(5)
41.00(6)
−27.16(9)
207
(
2 3 Pb

U. Herzog, G. Rheinwald / Journal of Organometallic Chemistry 648 (2002) 220–225
223
Table 4
pounds Me Si (E) MR (E=S, Se) with M constituting
a Group 14 element (C, Si, Ge, Sn, Pb) (see Table 2).
4
2
2
2
Crystal data of 1a as well as data collection and refinement details
1a
Empirical formula
Crystal shape
C16H22PbS Si
Plate
3. Experimental
2
2
Crystal color
Colorless
0.44×0.12×0.08
541.83
Triclinic
P1
(
3
.1. NMR and GC–MS measurements
Crystal size (mm)
Formula weight
Crystal system
Space group
All NMR spectra were recorded on a Bruker DPX
4
00 in CDCl solution and with TMS as internal stan-
3
13
Unit cell dimensions
1
29
dard for H, C and Si. External Me Sn, Ph Pb (l
−
CDCl were used as standards for Sn, Pb and Se.
,
)
)
)
8.709(2)
11.260(2)
11.607(2)
80.754(3)
72.789(3)
70.474(3)
1022.3(3)
2
4
4
Pb
a (A
b (A
c (A
,
2
178 ppm [16]) and Ph Se2 (l 460 ppm [17]) in
Se
19
1
207
77
,
3
h (°)
i (°)
k (°)
In order to obtain a sufficient signal-to-noise ratio of
29
2
1
1,2
2
Si-NMR spectra for resolving JSiC, JSiSe, J
or
SiSn
29
3
J
SiPb satellites Si INEPT spectra were also recorded.
V (A
Z
,
)
7
7
119
207
Se, Sn and Pb spectra were determined using an
Dcalc (g cm−3)
1.760
8.565
IGATED pulse program.
The assignment of C
supported by recording C APT spectra. Mass spectra
were measured on a Hewlett–Packard 5971 (ionization
energy 70 eV, column 30 m×0.25 mm×0.25 mm,
phenylmethylpolysiloxane, column temperature 80 °C
ipso
Linear absorption coefficient
in phenyl substituents was
−
1
(
mm
)
13
Scan method
ꢀ scans
Empirical
0.5474/0.1166
11 974
5769
4700
0.0356
Absorption correction
Max/min transmission
Measured reflections
Independent reflections
Observed reflections
Rint
−
1
−1
(
3 min)/20 K min , flow He 0.5 ml min ).
q range for collection (°)
Index ranges
1.84–30.88
−115h511, −155k515,
3.2. Crystal structure analysis
−
89.3
165l516
X-ray structure analysis measurements were per-
formed on a Bruker Smart 1k CCD area detector.
Crystal data of 1a as well as data collection and refine-
ment details are given in Table 4.
Completeness to q
(%)
max
2
a
Final R /wR (I\2|(I))
0.0296/0.0576
0.0435/0.0610
0.960
Geom./constr.
1.108/−1.148
1
2
a
Final R /wR (all data)
1
Goodness-of-fit (S) on F2
H-locating and refining
b
The unit cell dimensions were determined with the
program SMART [18]. For data integration and refine-
ment of the unit cell parameters the program SAINT [10]
was used. The space group was determined with the aid
of the programs ABSEN [19]. All data were corrected for
absorption applying SADABS [20]. The structures were
solved using direct methods (SIR97 [21]), refined using
least-squares-methods (SHELX-97 [22]) and drawn using
ZORTEP [23]. The ellipsoides at the non-hydrogen atoms
are at the 50% probability level.
Max/min e-density (e A
,
−3)
a
R =ꢀ(ꢁꢁF ꢁ−ꢁF ꢁꢁ)/ꢀꢁF ꢁ, wR =[ꢀ(w(F −F ) )/ꢀ(wF )]1/2), w=
2
2
2 2
c
2
o
1
o
c
o
o
2
?
2
2
2
1
/[| (F )+(aP) +bP] where P=(F +2F )/3.
o o c
b
2
o
2 2
c
1/2
S=[ꢀw(F −F ) ]/(n−p)
,
n=used reflections, p=used
parameters.
So far no cyclic chalcogenides containing silicon and
a Group 15 element are known. The reaction of a 1:1
molar mixture of ClSiMe –SiMe Cl and PhSbCl with
2
2
2
3.3. Starting materials
H S in the presence of a tertiary amine yielded the
2
antimony containing cycle 5a (Eq. (4)):
H S, sulfur, selenium, triethylamine, 1 M LiBEt H in
2
3
THF (super hydride), Ph SnCl , Ph Sb, SbCl and
2
2
3
3
Ph Pb were commercially available. Ph PbCl [24] was
4
2
2
(
4)
prepared by treatment of a stirred suspension of Ph Pb
4
in CHCl3 with a stream of dry HCl for 2 h. The
resulting white solid of Ph PbCl2 was filtered and
2
The corresponding selenium compound 5b emerged
from ClSiMe –SiMe Cl and PhSbCl on treatment with
washed with CHCl . THF was distilled from sodium
3
potassium alloy prior to use. The other solvents were
dried over KOH or sodium wire. All reactions were
carried out under argon applying standard Schlenk
techniques.
2
2
2
Li Se.
2
2
9
The Si-NMR shifts of 5a–b are remarkable because
they are some 10 ppm downfield from all related com-

224
U. Herzog, G. Rheinwald / Journal of Organometallic Chemistry 648 (2002) 220–225
3
.4. 5,5-Diphenyl-2,2,3,3-tetramethyl-1,4,2,3,5-
hexane. Removal of the solvent from the filtrate yielded
4a as a light yellow oil.
dithiadisilaplumbolane (1a) and 5,5-diphenyl-2,2,3,3-
tetramethyl-1,4,2,3,5-diselenadisilaplumbolane (2a)
119
77
29
Compound 4a: Sn-, Se- and Si-NMR: see Table
13
3
2
,
C-NMR: SiMe2 1.09 ( JSnC: 15.6 Hz), i 140.01
1
2
Compound 1a: 0.44 g (1 mmol) Ph PbCl and 0.19 g
( JSnC: 557.5 Hz), o 135.39 ( JSnC: 53.2 Hz), m 128.69
2
2
3
4
1
(
1 mmol) ClSiMe –SiMe Cl were dissolved in 15 ml
( JSnC: 66.5 Hz), p 129.76 ppm ( JSnC: 16.4 Hz); H-
NMR: 0.53 (SiMe ), 7.65 and 7.36 ppm (SnPh ).
Compound 4b: 0.345 g (1 mmol) Ph SnCl and 0.115
2
2
toluene and 0.62 ml (4.5 mmol) NEt were slowly added
while H S was bubbled through the stirred solution.
The reaction mixture turned black (some PbS) and a
precipitation of HNEt Cl occurred. After filtration, the
solvent was removed in vacuo to yield 1a as colorless
crystals, which could be recrystallized from hexane.
Compound 1a: Anal. Calc. for C H PbS Si (541.85
2
2
3
2
2
2
g (0.5 mmol) Cl SiMe–SiMeCl were dissolved in 1.5
2
2
ml THF and reacted with 2 mmol Li Se as described
2
3
above for 4a. Work-up as for 4a yielded 4b as a light
yellow solid product.
119
77
29
Compound 4b: Sn-, Se- and Si-NMR: see Table
1
6
22
2
2
13
3
−
1
2, C-NMR: SiMe 6.04 ( J : 15.7 Hz), i 139.33/
g mol ): C 35.47; H 4.09. Found: C 36.02; H 4.43%.
SnC
2
2
1
40.03, o 135.46 ( J : 53.2 Hz)/135.72 ( JSnC: 45.4
SnC
Compound 2a: 0.44 g (1 mmol) Ph PbCl and 0.19 g
2
2
3
3
Hz), m 128.67 ( J : 68.8 Hz)/128.93 ( JSnC: 67.3 Hz),
(
1 mmol) ClSiMe –SiMe Cl were dissolved in 3 ml
SnC
2
2
1
p 129.97/130.08 ppm; H-NMR: 1.00 ppm (SiMe),
toluene and this mixture (Ph PbCl forms a suspension)
was added to a suspension of 2 mmol Li Se (prepared
from 0.16 g (2 mmol) selenium powder and 4 ml of a 1
M solution of LiBEt H in THF). The reaction mixture
turned black (some PbSe). After reacting for 30 min the
solvents were removed in vacuo and replaced by 10 ml
toluene. After filtration the solvent was removed to
yield 2a as a light yellow oil.
2
2
7
.25–7.62 ppm (SnPh2).
2
Compound 4a as well as 4b contained small amounts
of (Ph SnSe) , which was proven by NMR
2
3
3
spectroscopy.
119
(
Ph SnSe) ,
Sn-NMR: −43.2 ppm (lit. −43.5
2
3
1
77
ppm [4]) J : 1318 Hz, Se-NMR: −435 ppm (lit.
SnSe
13
2
−
452 ppm [4]), C-NMR: i 139.91, o 135.39 ( JSnC:
3
5
(
3.9 Hz), m 128.57 ( JSnC: 70.4 Hz), p 129.65 ppm
JSnC: 12.3 Hz).
4
3.5. 3,3,7,7-Tetraphenyl-1,5-dimethyl-2,4,6,8-tetrathia-
3,7-diplumba-1,5-disilabicyclo[3.3.0]octane (1b) and
3,3,7,7-tetraphenyl-1,5-dimethyl-2,4,6,8-tetraselena-
3,7-diplumba-1,5-disilabicyclo[3.3.0]octane (2b)
3.7. 2-Phenyl-4,4,5,5-tetramethyl-1,3,2,4,5-dithiastiba-
disilolane, Me Si (S) SbPh (5a) and 2-phenyl-4,4,5,5-
4
2
2
tetramethyl-1,3,2,4,5-diselenastibadisilolane,
Me Si (Se) SbPh (5a)
4
2
2
Compound 1b: 0.44 g (1 mmol) Ph PbCl and 0.115
2
2
g (0.5 mmol) Cl SiMe–SiMeCl were dissolved in 15 ml
3.7.1. Phenyldichlorostibane, PhSbCl
About 4.56 g (20 mmol) SbCl and 3.53 g (10 mmol)
SbPh were mixed and heated to 100 °C for 3 h yield-
2
2
2
toluene and 0.62 ml (4.5 mmol) NEt were slowly added
3
3
while H S was bubbled through the stirred solution.
3
2
Work-up as described for 1a yielded 1b as a colorless
solid soluble in hexane, chloroform and toluene.
Compound 1b: Anal. Calc. for C H Pb S Si
ing an oily product. After cooling to room temperature
a NMR spectra of the product proved the formation of
13
PhSbCl2 ( C-NMR (ppm): i 151.87, o 132.77, m
26
26
2
4
2
1
−
1
1
7
(
(
29.43, p 131.43; H-NMR (ppm): o 7.75, m 7.47, p
(
937.31 g mol ): C 33.32; H 2.80. Found: C 32.98; H
13
.40) besides small amounts of Ph SbCl ( C-NMR
ppm): i 144.47, o 134.39, m 129.17, p 130.06; H-NMR
ppm): o 7.58, m 7.37, p 7.40).
3.23%.
2
1
Compound 2b: 0.44 g (1 mmol) Ph PbCl and 0.115
2
2
g (0.5 mmol) Cl SiMe–SiMeCl were dissolved in 3 ml
2
2
toluene and added to a suspension of 2 mmol Li Se as
described above for 2a. An analogous work-up yielded
2
3
.7.2. Me Si (S) SbPh (5a)
About 0.27 g (1 mmol) PhSbCl and 0.19 g (1 mmol)
4
2
2
2b as a light yellow oil.
2
ClSiMe –SiMe Cl were dissolved in 20 ml toluene and
2
2
0
.55 ml (4 mmol) NEt3 were slowly added while a
3
.6. 5,5-Diphenyl-2,2,3,3-tetramethyl-1,4,2,3,5-
stream of H S was bubbled through the stirred solu-
tion. After filtration from the precipitated HNEt Cl the
solvent was removed in vacuo yielding 5a as a light
yellow oily residue.2
2
diselenadisilastannolane (4a) and 3,3,7,7-tetraphenyl-
,5-dimethyl-2,4,6,8-tetraselena-3,7-distanna-1,5-
3
1
disilabicyclo[3.3.0]octane (4b)
9
13
Compound 5a: Si-NMR: see Table 2, C-NMR
Compound 4a: 0.345 g (1 mmol) Ph SnCl and 0.19 g
(ppm): 3.04/2.24 (SiMe ), i 145.10, o 134.18, m 128.63,
p 129.33; H-NMR: 0.12/0.40 (SiMe ), 7.75 (ortho),
2
2
2
1
(
1 mmol) ClSiMe –SiMe Cl were dissolved in 1.5 ml
2
2
2
THF and added to a suspension of 2 mmol Li Se in
THF (prepared as described above). After 30 min the
solvents were removed in vacuo and replaced by 10 ml
7.38 (meta+para). +
2
GC–MS: 378 (M , 3), 363 (M−Me, 1), 301 (M−
Ph, 1), 290 (PhSbS Si, 2), 258 (PhSbSSi, 1), 228
2

U. Herzog, G. Rheinwald / Journal of Organometallic Chemistry 648 (2002) 220–225
225
(
SbS SiMe, 4), 198 (PhSb, 9), 165 (S Si Me , 10), 135
References
2
2
2
3
(
PhSiMe , 100), 121 (Sb, 2), 73 (SiMe , 22).
2
3
[
[
1] U. Herzog, G. Rheinwald, J. Organomet. Chem. 627 (2001) 23.
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3
.7.3. Me Si (Se) SbPh (5b)
4
2
2
About 0.27 g (1 mmol) PhSbCl and 0.19 g (1 mmol)
2
[
3] P. Boudjouk, S.R. Bahr, D.P. Thompson, Organometallics 10
ClSiMe –SiMe Cl were dissolved in 1 ml THF. This
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2
2
2
(
1991) 778.
2
[4] S.R. Bahr, P. Boudjouk, G.J. McCarthy, Chem. Mater. 4
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3
[
[
[
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of the solvent in vacuo yielded 5b as a light yellow oily
residue.
(
2
2
9
77
Compound 5b: Si- and Se-NMR: see Table 2,
1
3
C-NMR (ppm): 3.18/1.90 (SiMe ), i 139.76, o 135.03,
2
[9] M. Dr a¨ ger, A. Blecher, H.-J. Jacobsen, B. Krebs, J.
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1
m 128.50, p 128.97; H-NMR: 0.20/0.48 (SiMe ), 7.81
2
(
ortho), 7.32 (meta+para).
[10] A. Blecher, M. Dr a¨ ger, Angew. Chem. 91 (1979) 740.
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Crystallographic data (excluding structure factors)
for 1a have been deposited at the Cambridge Crystallo-
graphic Data Centre as supplementary publication no.:
CCDC no. 172656. Copies of the data can be obtained,
free of charge, on application to The Director, CCDC,
[
12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44-
[
[
[
[
1223-336033 or e-mail: deposit@ccdc.cam.ac.uk or
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Acknowledgements
The authors thank the Deutsche Forschungsgemein-
schaft for financial support. Special thanks are given to
Professor H. Lang, Chair of Inorganic Chemistry, TU
Chemnitz for the access to the X-ray facility used to
determine the single crystal structures.
[
[
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L. Zsolnai, G. Huttner, Germany: University of
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