A general route to alkylene-, arylene-, or benzylene-bridged ditin hexachlorides and hexaalkynides

Article abstract of DOI:10.1021/om0202468

The preparation of alkylene-, arylene-, or benzylene-bridged ditin hexachlorides in high yields from the reaction of the corresponding hexacyclohexylated compounds with tin tetrachloride is described. The tetragonal geometry of the tin atom of 1,4-bis(trichlorostannyl)-butane in the solid state indicates that no intramolecular or intermolecular interaction involving either end of the molecule exists in this compound. The ditin hexachlorides were successfully transformed in the corresponding hexaalkynides, precursors of hybrid materials.

Full text of DOI:10.1021/om0202468

4590
Organometallics 2002, 21, 4590-4594
A Gen er a l Rou te to Alk ylen e-, Ar ylen e-, or
Ben zylen e-Br id ged Ditin Hexa ch lor id es a n d
Hexa a lk yn id es
Bernard J ousseaume,* Hocine Riague, and Thierry Toupance
Laboratoire de Chimie Organique et Organome´tallique, UMR 5802, Universite´ Bordeaux I,
351 Cours de la Libe´ration, 33405 Talence, France
Mohamed Lahcini
De´partement de Chimie, Universite´ Cadi Ayyad, Marrakech, Morocco
Philip Mountford and Ben R. Tyrrell
Inorganic Chemistry Laboratory, University of Oxford, South Parks Road,
Oxford, U.K. OX1 3QR
Received March 29, 2002
The preparation of alkylene-, arylene-, or benzylene-bridged ditin hexachlorides in high
yields from the reaction of the corresponding hexacyclohexylated compounds with tin
tetrachloride is described. The tetragonal geometry of the tin atom of 1,4-bis(trichlorostannyl)-
butane in the solid state indicates that no intramolecular or intermolecular interaction
involving either end of the molecule exists in this compound. The ditin hexachlorides were
successfully transformed in the corresponding hexaalkynides, precursors of hybrid materials.
Since they were first described in 1957,1,2 distanny-
oxides or halides. However, the described preparations
are limited to distannylalkyl derivatives where the
strong tin-alkyl bonds allow the linkage between both
tins to be preserved.
lated derivatives have received much attention. 1,2-
Hexaorganodistannylated compounds have interesting
applications in the Stille reaction,3 while 1,n-haloorga-
nodistannylated species have been mainly studied as
Lewis acids due to their ability to complex anions.4
Several methods of preparation have been described,
depending on the nature of the linker between the metal
atoms. When the two tins are separated by an alkyl or
alkenyl chain, they can be incorporated either at the
same time or successively. In the first case, the more
straightforward way involves either the coupling of a
triorganostannylmetal with a dihalide5 or the coupling
of a di-Grignard or a dilithium reagent with a triorga-
notin halide.6 Bis(stannyl)acetylenes can be prepared
from a triorganotin halide and CaC2 with ultrasound.7
However, when these dimetallic species are not avail-
able, the palladium-catalyzed8 or noncatalyzed9 addition
of a hexaorganoditin to unsaturated compounds can be
successfully performed. The second case mainly involves
the hydrostannation of an unsaturated tetraorganotin
compound.2 When the two tins are separated by an aryl
ring, it is possible to use a cycloaddition reaction,10 the
coupling of a di-Grignard or a dilithium reagent with
an triorganotin halide,11 or a triorganostannylmetal
with an aryl halide.12 Then classical electrophilic reac-
tions allow facile transformation to the corresponding
(4) (a) Swami, K.; Hutchinson, J . P.; Kuivila, H. G.; Zubieta, J . A.
Organometallics 1984, 3, 1687. (b) Hyde, J . R.; Karol, T. J .; Hutchinson,
J . P.; Kuivila, H. G.; Zubieta, J . A. Organometallics 1982, 1, 404. (c)
Karol, T. J .; Hutchinson, J . P.; Hyde, J . R.; Kuivila, H. G.; Zubieta, J .
A. Organometallics 1983, 2, 106. (d) Kuivila, H. G.; Karol, T. J .; Swami,
K. Organometallics 1983, 2, 909. (e) Austin, M.; Gebreyes, K.; Kuivila,
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10.1021/om0202468 CCC: $22.00 © 2002 American Chemical Society
Publication on Web 09/28/2002

Bridged Ditin Hexachlorides and Hexaalkynides
Organometallics, Vol. 21, No. 22, 2002 4591
We have been interested recently in the preparation
of organotin precursors of hybrid materials,13 which
allowed us to present a new route to functional mono-
organotins.14 To broaden the scope of the avaliable
precursors, as the corresponding disilylated compounds
revealed excellent precursors of various types of mi-
croporous or mesoporous silica,15 monoorganodistanny-
lated compounds were needed. The classical method of
preparation involving the electrophilic cleavage of phen-
yl groups in R,ω-bis(triphenyltin)alkanes has been very
successfully applied for the preparation of alkylene-
bridged ditin chlorides, studied due to their strong
ability to form chelate complexes with anions. It cannot
be applied to an aryl- or a benzyl-type linker, where the
electrophilic cleavage would not be selective enough and
would also cleave tin-bridge bonds, which would greatly
reduce the yields. Here we present a general route to
alkylene-, arylene-, or benzylene-bridged ditin com-
pounds based on the use of auxiliary cyclohexyl groups.
The first crystal structure of an uncomplexed poly-
methylene-bridged ditin hexachloride is also reported.
bis(tricyclohexylstannyl)benzene (5) was isolated in 65%
yield.
In the case of benzylene-bridged ditins, the method
described above was only suitable for 1,2-disubstituted
compounds, where the corresponding di-Grignard re-
agent is available. For the 1,4-disubstituted compound,
a Barbier-type reaction was more appropriate, as the
corresponding di-Grignard reagent is not very stable.
Resu lts a n d Discu ssion
Subsequent treatment of these distannylated with tin
tetrachloride afforded the corresponding hexachlorides
in good yields. In the case of benzylic halides, the
reaction had to be conducted at lower temperature to
obtain good yields.
To prepare hydrolyzable alkylene-, arylene-, or benz-
ylene-bridged hexaalkynylditins, precursors of hybrid
alkylene-, arylene-, or benzylene-bridged tin oxide ma-
terials, it is necessary to have the corresponding
hexachlorides. To obtain these species, the successful
preparation of functional organotin trichlorides from the
electrophilic reaction of the corresponding tricyclohex-
ylorganotin with tin tetrachloride was used. A series of
R,ω-dibromoalkanes was subjected to the reaction with
an excess of magnesium, and then, a solution of tricy-
clohexyltin chloride was added. That allowed the isola-
tion of alkylene-bridged hexacyclohexylditins in good
yields with four, five, six, or ten methylene groups
between the metals.
With 1,4-bis(tricyclohexylstannyl)benzene the reac-
tion was slower than with other compounds and oc-
curred stepwise. It was thus possible to isolate a mixed
compound, 1-(trichlorostannyl)-4-(tricyclohexylstannyl)-
benzene, 15, characterized by 119Sn NMR spectroscopy
by two peaks at -61.1 and -102.0 ppm, corresponding
to the trichlorostannyl and to the tricyclohexylstannyl
moiety, respectively. Alkylation with methylmagnesium
chloride afforded 1-(tricyclohexylstannyl)-4-(trimethyl-
stannyl)benzene, 16, confirming the presence of an
unsymmetrical compound.
This reaction was successfully extended to the prepa-
ration of phenylene-bridged hexacylohexylditins, as 1,4-
(11) Boue, S.; Gielen, M.; Nasielski, J . Bull. Soc. Chim. Belg. 1967,
76, 559. J uara, K. L.; Hundal, H. S.; Handa, R. D. Indian J . Chem.
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C.; J ordens, F.; J ousseaume, B.; Niesel, T. J . Inorg. Organomet. Polym.
1998, 8, 48. J aumier, P. J ousseaume, B.; Riague, H.; Toupance, T.;
Lahcini, M. In Hybrid Organic/ Inorganic Materials; Laine, R. M.,
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F. Organometallics 1995, 14, 685. J ousseaume, B.; Lahcini, M.;
Fouquet, E.; Barbe, B. J . Org. Chem. 1994, 59, 8292. Biesemans, M.;
Willem, R.; Damoun, S.; Geerlings, P.; Lahcini, M.; J aumier, P.;
J ousseaume, B. Organometallics 1996, 15, 2237. J aumier, P.; J ous-
seaume, B.; Tiekink, E. R. T. Biesemans, M.; Willem, R. Organome-
tallics 1997, 16, 5124. Biesemans, M.; Willem, R.; Damoun, S.;
Geerlings, P.; Tiekink, E. R. T.; Lahcini, M.; J aumier, P.; J ousseaume,
B. Organometallics 1998, 17, 90. J aumier, P. J ousseaume, B.; Lahcini,
M.; Ribot, F.; Sanchez, C. J . Chem. Soc., Chem. Commun. 1998, 369.
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Lahcini, M.; J aumier, P.; J ousseaume, B. Angew. Chem., Int. Ed. 1999,
32, 402. Willem, R.; Biesemans, M.; J aumier, P.; J ousseaume, B. J .
Organomet. Chem. 1999, 572, 233.
The lower reactivity of the mixed compound was
explained by a deactivation of the phenyl-tricyclohexyl-
stannyl bond toward the electrophilic cleavage of tin

4592 Organometallics, Vol. 21, No. 22, 2002
Ta ble 1. Selected In ter a tom ic (Å, d eg) P a r a m eter s for [Cl3Sn (CH2)4Sn Cl3]a
J ousseaume et al.
Sn(1)-Cl(1)
Sn(1)-Cl(2)
Sn(1)-Cl(3)
Sn(1)-C(1)
C(1)-C(2)
2.289(2) [2.376(2)]
2.417(3) [2.236(3)]
2.3106(11)
2.128(3)
1.514(4)
1.534(5)
2.3009(9)
2.402(4) [2.272(4)]
2.3260(7)
2.132(3)
1.520(4)
Cl(2)-Sn(1)-Cl(3)
Cl(1)-Sn(1)-C(1)
Cl(2)-Sn(1)-C(1)
Cl(3)-Sn(1)-C(1)
Sn(1)-C(1)-C(2)
C(1)-C(2)-C(2A)
Cl(4)-Sn(2)-Cl(5)
Cl(4)-Sn(2)-Cl(6)
Cl(5)-Sn(2)-Cl(6)
Cl(4)-Sn(2)-C(3)
Cl(5)-Sn(2)-C(3)
Cl(6)-Sn(2)-C(3)
Sn(2)-C(3)-C(4)
C(3)-C(4)-C(4B)
104.88(9) [101.5(1)]
112.2(1) [114.8(1)]
115.35(11) [127.19(11)]
110.32(8)
111.4(2)
111.0(3)
110.17(9) [97.79(8)]
103.17(3)
97.50(9) [104.1(1)]
122.65(8)
107.94(12)
112.50(8)
C(2)-C(2A)
Sn(2)-Cl(4)
Sn(2)-Cl(5)
Sn(2)-Cl(6)
Sn(2)-C(3)
C(3)-C(4)
C(4)-C(4B)
1.535(5)
110.5(2)
110.1(3)
Cl(1)-Sn(1)-Cl(2)
Cl(1)-Sn(1)-Cl(3)
101.16(12) [104.7(1)]
112.49(9) [91.90(8)]
a
Where relevant, the corresponding values for the other distorted component (i.e., Cl(11), Cl(21), and Cl(51) for atoms Cl(1), Cl(2), and
Cl(5), respectively) are given in square brackets.
tetrachloride by the electron-withdrawing trichlorostan-
nyl group situated in para position. A longer reaction
time or moderate heating of the reaction mixture
ensured the transformation of the remaining tricyclo-
hexylstannyl group into the trichlorostannyl group. This
electronegative effect was expressed in the strong
coordination of the tins by acetonitrile, used in the
acetonitrile/pentane extraction method, which could not
be removed totally under vacuum. However, displace-
ment of acetonitrile with a large excess of THF followed
by evaporation of THF led to the unsolvated hexachlo-
ride. The same phenomenon occurred with 1,2- and 1,4-
bis(trichlorostannylmethyl)benzene. An extra washing
with THF was necessary to displace the acetonitrile,
unsuitable for the next alkynylation with alkynyllithi-
ums.
The question arose about an eventual internal coor-
dination of the tins by chlorine atoms. To maximize the
possible effects,16 1,4-bis(trichlorostannyl)butane, a com-
pound susceptible to form the smallest rings by in-
tramolecular coordination, which induces the stronger
coordination, was chosen to be studied by X-ray crystal-
lography. This is the first crystallographic structure of
free hexachlorodistannylated compounds, known stuc-
tures recently described being chloride,4t DMSO,17 or
water4s,18 adducts. The atomic arrangements and the
crystallographic numbering are shown in Figure 1.
Selected interatomic parameters are listed in Table 1.
The molecules lie across crystallographic inversion
centers, and the asymmetric unit contains two halves
of two independent molecules. Three of the chlorine
atoms were disordered, which precludes any discussion
about the geometry of the tin (for further details, see
the Supporting Information). Nevertheless, it is clear
F igu r e 1. Molecular structure of Cl3Sn(CH2)4SnCl3.
that both of the tin centers are tetracoordinated, as in
uncoordinated trichloroorganotins, and do not interact
with each other by bridging chlorine atoms. The shortest
intermolecular tin-chlorine distance (5.17 Å) is well
outside the appropriate sum of their van der Waals radii
(3.97 Å). The butylene group is not extended, as seen
in the expanded angles subtended at each CH2CH2Sn
carbon of 111.0(3)° and 110.1(3)° instead of ca. 114° in
1,4-bis(trichlorostannyl)butane, 2 benzyltriphenylphos-
phonium chloride.4t
Then alkynylation of the hexachlorides with propyn-
yllithium or phenylethynyllithium gave the correspond-
ing alkynides in good yields. To the best of our knowl-
edge, ditin hexaalkynides are described here for the first
time They were subsequently hydrolyzed in THF to give
transparent or opaque gels, depending on the nature of
(15) Shea, K. J .; Loy, D. A. Chem. Mater. 2001, 13, 3306. Shea, K.
J .; Loy, D. A. Acc. Chem. Res. 2001, 34, 707. Loy, D. A.; Shea, K. J .
Chem. Rev. 1995, 95, 1431. Cerveau, G.; Corriu, R. J . P.; Framery, E.
Chem. Mater. 2001, 13, 3373. Corriu, R. J . P. Angew. Chem., Int. Ed.
2000, 39, 1376.
(16) J ousseaume, B.; Villeneuve, P. J . Chem. Soc., Chem. Commun.
1987, 517. J ousseaume, B.; Villeneuve, P.; Draeger, M.; Roller, S.;
Chezeau, J . M. J . Organomet. Chem. 1988, 349, C1. Biesemans, M.;
Willem, R.; Damoun, S.; Geerlings, P.; Lahcini, M.; J aumier, P.;
J ousseaume, B. Organometallics 1996, 15, 2237. J aumier, P.; J ous-
seaume, B.; Tiekink, E. R. T. Biesemans, M.; Willem, R. Organome-
tallics 1997, 16, 5124. Biesemans, M.; Willem, R.; Damoun, S.;
Geerlings, P.; Tiekink, E. R. T.; Lahcini, M.; J aumier, P.; J ousseaume,
B. Organometallics 1998, 17, 90.
(17) Dakternieks, D.; Zobel, B.; Tiekink, E. R. T. Main Group Met.
Chem. 2000, 23, 253.
(18) Dakternieks, D.; Zobel, B.; Tiekink, E. R. T. Main Group Met.
Chem. 2000, 23, 321.

Bridged Ditin Hexachlorides and Hexaalkynides
Organometallics, Vol. 21, No. 22, 2002 4593
Ta ble 2. Cr ysta l Da ta a n d Str u ctu r e Refin em en t
for [Cl3Sn (CH2)4Sn Cl3]
1,4-Bis(tr icycloh exylsta n n yl)bu ta n e, 1: mp 235 °C; 71%
yield; 1H δ 0.7-0.9 (m, 4H); 1.1-2.0 (m, 70H). 13C δ 7.1 [276];
26.3 [320]; 27.5 [7]; 29.8 [52]; 32.8 [16]; 33.3; 119Sn δ -64.9.
Anal. Calcd for C40H74Sn2: C, 60.63; H, 9.41; Sn, 29.96.
Found: C, 60.63; H, 9.41; Sn, 29.96.
empirical formula
fw
C4 H8Cl6Sn2
506.21
cryst description
cryst size, mm
temperature, K
cryst syst
space group
a, Å
colorless block
0.30 × 0.20 × 0.20
150
triclinic
P1h
7.7894(2)
7.9828(2)
11.7951(2)
98.027(1)
105.393(1)
98.9022(8)
685.92(3)
2
1,5-Bis(tr icycloh exylsta n n yl)p en ta n e, 2: mp 150 °C;
61% yield; 1H δ 0.70-0.90 (m, 4H); 1.10-1.95 (m, 72H); 13C δ
6.9 [269]; 26.3 [320]; 26.9 [20]; 27.7 [11]; 29.7 [51]; 32.8 [15];
40.4 [48]; 119Sn δ -65.2. Anal. Calcd for C41H76Sn2: C, 61.07;
H, 9.50; Sn, 29.44. Found: C, 60.83; H, 9.59; Sn, 28.41.
1,6-Bis(tr icycloh exylsta n n yl)h exa n e, 3: mp 157 °C; 58%
b, Å
c, Å
1
yield; H δ 0.6-1.0 (m, 4H); 1.1-2.0 (m, 74H); 13C δ 7.0; 25.9
R, deg
[308]; 27.4 [15]; 29.4 [62]; 32.2; 32.5 [21]; 34.6; 119Sn δ -65.3.
Anal. Calcd for C42H78Sn2: C, 61.49; H, 9.58; Sn, 28.93.
Found: C, 61.11; H, 9.48; Sn, 29.06.
â, deg
γ, deg
V, Å
Z
D
1,10-Bis(tr icycloh exylsta n n yl)d eca n e, 4: mp 182 °C;
calc, g cm-1
2.45
1
61% yield; H δ 0.7-0.9 (m, 4H); 1.1-2.0 (m, 82H); 13C δ 7.0;
F(000)
466.15
4.76
26.0 [317]; 27.5 [8]; 29.1 [5]; 29.5 [53]; 29.9; 32.6 [16]; 35.5;
40.1; 119Sn δ -65.8. Anal. Calcd for C46H86Sn2: C, 63.03; H,
9.89; Sn, 27.08. Found: C, 63.54; H, 9.74; Sn, 27.62.
1,4-Bis(tr icycloh exylsta n n yl)ben zen e, 5: mp 125 °C;
65% yield; 1H δ 1.1-1.9 (m, 66H); 8.07 (s, 4H, [29]); 13C δ 25.5
[320]; 27.6; 29.9 [60]; 33.0 [18]; 137.8; 141.0; 119Sn δ -104.4.
Anal. Calcd for C42H70Sn2: C, 62.10; H, 8.69; Sn, 29.22.
Found: C, 62.85; H, 8.94; Sn, 28.35.
1,2-Bis(t r icycloh exylst a n n ylm et h yl)ben zen e, 6. The
Grignard reagent was prepared from the corresponding dichlo-
ride: mp 129 °C; 69% yield; 1H δ 1.1-1.9 (m, 66H); 2.3 (s, 4H,
[52]); 6.80-6.95 (m, 4H); 13C δ 14.4 [214]; 27.3 [304]; 27.4; 29.5
[55]; 32.3 [16]; 123.2; 127.9; 139.0; 119Sn δ -75.9 [60]. Anal.
Calcd for C44H74Sn2: C, 62.88; H, 8.87; Sn, 28.24. Found: C,
62.71; H, 8.92; Sn, 28.63.
µ, mm-1
θ, deg
2.91-27.48
-10 e h e 9
-10 e k e 10
0 e l e 15
5741
index ranges
no. of data colld
no. of unique data
2728
with I ) 3.0σ(I)
R
0.026
0.025
Rw
the spacer, which were then thermolyzed, furnishing
high surface area mesoporous tin oxide.19
Con clu sion
1,4-Bis(tr icycloh exylsta n n ylm eth yl)ben zen e, 7. In this
case, a solution of 9.45 g (54 mmol) of 1,4-bis(chloromethyl)-
benzene and 40 g (99 mmol) of tricyclohexylchloroethane in
THF (175 mL) was slowly added to magnesium (5.2 g, 214
It has been shown that alkylene-, arylene-, or ben-
zylene-bridged hexacyclohexylditins react with tin tet-
rachloride under mild conditions to give the correspond-
ing hexachlorides in quantitative yields. The strong tin-
cyclohexyl bond makes the tricyclohexyltin group very
useful in this case, allowing the facile preparation of
ditin hexachlorides with fragile tin-phenyl or tin-
benzyl bonds. The crystal structure of 1,4-bis(trichlo-
rostannyl)butane revealed that no interaction exists
between the two trichlorotin groups. Applications of the
corresponding hexaalkynides to the preparation of me-
soporous tin oxide are in progress.
1
mmol) and THF (250 mL): mp 117 °C; 78% yield; H δ 1.1-
1.9 (m, 66H); 2.2 (s, 4H [56]); 6.85 (s, 4H); 13C δ 14.9 [209];
26.8 [318]; 27.4; 29.4 [55]; 32.5 [16]; 127.4 [19]; 137.8; 119Sn δ
-76.29 [58]. Anal. Calcd for C44H74Sn2: C, 62.88; H, 8.87; Sn,
28.24. Found: C, 62.29; H, 8.85; Sn, 29.40.
Gen er a l P r oced u r e for th e P r ep a r a tion of Bis(tr ich lo-
r osta n n yl)a lk yl a n d -a r yl Der iva tives. SnCl4 (8.8 mL, 75
mmol) was slowly added to a solution of bis(tricyclohexylstan-
nylated) compound (29 mmol) in toluene (60 mL). After stirring
at 70 °C for 15 h, the solvent was evaporated under reduced
pressure. Acetonitrile (50 mL) was added. The solution was
extracted with petroleum ether (5 × 20 mL) to remove
tricyclohexyltin chloride. Acetonitrile was evaporated to give
the pure hexachloride.
Exp er im en ta l Section
All reactions were carried out under a nitrogen atmosphere.
Pentane, THF, and diethyl ether were distilled from sodium
benzophenone ketyl prior use. Acetonitrile was distilled over
CaH2. Tin tetrachloride was distilled before use. 1H and 13C
NMR spectra were recorded on a Bruker AC-250 spectrometer
(solvent CDCl3), and 119Sn NMR spectra were recorded on a
Bruker DPX-200 spectrometer (solvent CDCl3). Tin-hydrogen
and tin-carbon coupling constants are given in square brack-
ets.
Gen er a l P r oced u r e for th e P r ep a r a tion of Bis(tr icy-
cloh exylsta n n yl)a lk yl a n d -a r yl Der iva tives. A solution
of alkyl or aryl dibromide (59 mmol) in THF (80 mL) was
slowly added to magnesium (3.0 g, 125 mmol) in THF (10 mL).
The mixture was refluxed for 30 min and cooled at room
temperature, and a solution of triclohexyltin chloride (39.43
g, 97.8 mmol) in THF (150 mL) was added. After refluxing for
1 h the mixture was hydrolyzed with a saturated solution of
NH4Cl, extracted with petroleum ether (100 mL), and dried
with MgSO4, and the solvents were evaporated. Recrystalli-
zation from petroleum ether gave the pure products.
1,4-Bis(tr ich lor osta n n yl)bu ta n e,4s 8: mp 58 °C; 94%
yield; 1H δ 2.45 (m, 4H); 2.73(m, 4H); 13C δ 27.6 [55, 141]; 31-
[8, 700]; 119Sn δ 5.1.
1,5-Bis(tr ich lor osta n n yl)p en ta n e,4s 9: viscous liquid; 93%
1
yield; H δ 1.67 (m, 2H); 2.02 (quint, 4H); 2.42 (t, 4H, [85]);
13C δ 24.4 [58]; 32.4 [662]; 34.8 [126]; 119Sn δ 4.0.
1,6-Bis(tr ich lor osta n n yl)h exa n e, 10: viscous liquid; 97%
1
yield; H δ 1.94 (m, 4H); 2.33 (m, 4H); 2.75 (m, 4H, [86]); 13C
δ 24.8 [57]; 31.9 [111]; 32.8 [659]; 119Sn δ 3.0. Anal. Calcd for
C6H12Cl6Sn2: C, 13.49; H, 2.26; Sn, 44.43. Found: C, 14.14;
H, 2.61; Sn, 45.24.
1,10-Bis(tr ich lor osta n n yl)d eca n e, 11: viscous liquid; 98%
yield; 1H δ 1.2-1.6 (m, 12H); 1.85-2.05 (m, 4H); 2.42 (t, 4H);
13C δ 25.0 [78]; 29.2; 29.5; 32.9 [135]; 33.8 [807]; 119Sn δ 5.9.
Anal. Calcd for C10H20Cl6Sn2: C, 20.35; H, 3.41; Sn, 40.21.
Found: C, 19.81; H, 3.87; Sn, 41.15.
1,4-Bis(tr ich lor osta n n yl)ben zen e, 12. The poor solubility
of the hexachloride required the use of 200 mL of acetonitrile.
The solid was solubilized in THF, and the solvent evapo-
1
rated: mp 135 °C; 95% yield; H δ 7.80 (s, 4H [55, 130]); 13C
(19) J ousseaume, B.; Riague, E.; Toupance, T. To be published.
δ 118.0 [60, 110]; 136.0; 119Sn δ -66.3. Anal. Calcd for C6H4-

4594 Organometallics, Vol. 21, No. 22, 2002
J ousseaume et al.
Cl6Sn2: C, 13.70; H, 0.77; Sn, 45.11. Found: C, 14.54; H, 1.03;
Sn, 45.91. Anal. Calcd for C8H8Cl6Sn2: C, 17.34; H, 1.45; Sn,
42.83. Found: C, 17.75; H, 1.63; Sn, 42.07.
1,2-Bis(tr ip r op -1-yn ylsta n n ylm eth yl)ben zen e, 20: mp
122 °C; 61% yield; 1H δ 2.2 (s, 18H [15]); 3.05 (s, 4H [96]);
7.3-7.5 (m, 4H); 13C δ 5.5 [16]; 22.2 [570]; 75.0 [880]; 108.7
[178]; 125.7 [21]; 129.5 [20, 42]; 135.2; 119Sn δ -266.4. Anal.
Calcd for C26H26Sn2: C, 54.23; H, 4.55; Sn, 41.22. Found: C,
53.31; H, 4.78; Sn, 42.05.
1,2-Bis(tr ich lor osta n n ylm eth yl)ben zen e, 13. The addi-
tion of tin tetrachloride was conducted at -30 °C: mp 86 °C;
1
90% yield; H δ 4.68 (s, 4H, [116]); 8.28 (m, 4H); 13C δ 44.8;
136.5; 148.6; 151.0; 119Sn δ -62.2. Anal. Calcd for C8H8Cl6-
Sn2: C, 17.34; H, 1.45; Sn, 42.83. Found: C, 17.75; H, 1.63;
Sn, 42.07.
1,4-Bis(tr ip r op -1-yn ylsta n n ylm eth yl)ben zen e, 21: mp
109 °C; 62% yield; 1H δ 1.85 (s, 18H [18]); 2.65 (s, 4H [14, 130]);
7.05 (s, 4H); 13C δ 5.1 [20]; 27.3 [554]; 76.2 [849]; 106 [216];
128.2 [26, 50]; 134.3 [32]; 119Sn δ -263.6. Anal. Calcd for
1,4-Bis(tr ich lor osta n n ylm eth yl)ben zen e, 14. The addi-
tion of tin tetrachloride was conducted at -30 °C. Recrystal-
lized from THF/CH2Cl2: mp 73 °C; 89% yield; 1H δ 4.05 (s,
4H, [20, 115]); 7.65 (s, 4H); 13C δ 40.9; 150.0; 153.1; 119Sn δ
-33.7. Anal. Calcd for C8H8Cl6Sn2: C, 17.34; H, 1.45; Sn, 42.83.
Found: C, 16.61; H, 1.29; Sn, 41.13.
C
26H26Sn2: C, 54.23; H, 4.55; Sn, 41.22. Found: C, 53.74; H,
4.36; Sn, 41.95.
X-r a y Cr ysta llogr a p h y. Crystal data collection and pro-
cessing parameters are given in Table 1. Crystals were
immersed in a film of perfluoropolyether oil on a glass fiber
and transferred to a Nonius Kappa-CCD diffractometer
equipped with an Oxford Cryosystems low-temperature de-
vice.20 Data were collected at 150 K using Mo KR radiation.
The images were processed and equivalent reflections were
merged; corrections for Lorentz-polarization and absorption
were applied.21 The structure was solved by direct methods,22
and subsequent Fourier difference syntheses revealed the
positions of all other non-hydrogen atoms. The asymmetric
unit contains two halves of crystallographically independent
molecules of [Cl3Sn(CH2)4SnCl3], with each molecule lying
across a crystallographic inversion center. After preliminary
anisotropic refinements three Cl atoms gave elongated dis-
placement ellipsoids. These atoms were subsequently “split”,
modeled in terms of static 50:50 disorder [Cl(1) & Cl(11); Cl-
(2) & Cl(21); Cl(5) & Cl(51)], and refined in the anisotropic
approximation. H atoms were placed in calculated positions
and refined in a riding model. An extinction correction23 and
Chebychev weighting scheme24 were applied in the final stages
of refinement. All crystallographic calculations were performed
using SIR9222 and CRYSTALS.25
1-(Tr ich lor ost a n n yl)-4-(t r icycloh e xylst a n n yl)b e n -
zen e, 15. The addition of 1 equiv of tin tetrachloride was
conducted at -30 °C. After extraction with toluene the
compound was recovered as a solid contaminated with some
tricyclohexyltin chloride: 1H δ 1.1-1.9 (m, 33H); 7.42 (m, 4H)-
;
13C δ 27.4; 27.6; 29.7; 32.7; 127.8; 135.1; 136.8; 147.3; 119Sn
δ -61.1; -102.0.
1-(Tr icycloh e xylst a n n yl)-4-(t r im e t h ylst a n n yl)b e n -
zen e, 16. To a solution of crude 12 (6.69 g, 10 mmol) in THF
at 0 °C was added a solution of MeMgI (60 mmol) in diethyl
ether. After stirring for 2 h at room temperature, the solution
was hydrolyzed and dried, the solvents were evaporated, and
16 was recovered as an oil after chromatography on silica gel:
1
84% yield; H δ 0.47 (s, 9H), 1.1-1.9 (m, 33H); 7.94 (m, 4H);
13C δ -9.5; 26.6; 27.5; 29.6; 32.8; 135.1; 137.5; 141.3; 141.9;
119Sn δ -29.6; -104.4. Anal. Calcd for C27H46Sn2: C, 53.33;
H, 7.63; Sn, 39.04. Found: C, 53.87; H, 7.95; Sn, 38.43.
Gen er al P r ocedu r e for th e P r epar ation of Bis(tr ialkyn -
ylsta n n yl)a lk yl a n d -a r yl Der iva tives. To a solution of
phenylacetylene (22.85 g, 224 mmol) (or propyne, 400 mmol)
in toluene (50 mL) at -78 °C was slowly added a solution of
butyllithium in hexanes (81.6 mL, 204 mmol). After 15 min
stirring at room temperature, a solution of 1,5-bis(trichlo-
rostannyl)pentane (14.6 g, 28 mmol) in toluene (60 mL) was
added at -78 °C. The suspension was then heated at 70 °C
for 12 h. The suspension was filtered on dry MgSO4 under dry
N2 and the toluene evaporated. The solids were recrystallized
from toluene.
Ack n ow led gm en t. The authors are grateful to
Sipcam Phyteurop for a generous gift of chemicals.
Su p p or tin g In for m a tion Ava ila ble: Tables with bond
lengths, bond angles, atomic coordinates, and anisotropic
displacement parameters for the structures of 8. This in-
formation is available free of charge via the Internet at
http://pubs.acs.org.
1,4-Bis(tr ip r op -1-yn ylsta n n yl)bu ta n e, 17: mp 95 °C;
1
59% yield; H δ 1.54 (t, 4H [78]); 2.04 (m, 4H); 2.21 (s, 18H
[15]); 13C δ 5.6 [16]; 14.6 [650]; 29.0 [30, 94]; 76.9 [810]; 108.1
[168]; 119Sn δ -252 [30]. Anal. Calcd for C22H26Sn2: C, 50.06;
H, 4.97; Sn, 44.97. Found: C, 49.33; H, 4.90; Sn, 46.18.
1,5-Bis(tr is(p h en yleth yn yl)sta n n yl)p en ta n e, 18: mp
127 °C; 79% yield; 1H δ 1.64 (t, 4H); 1.80 (m, 4H); 2.00 (quint,
4H); 7.35 (m, 12H); 7.59 (m, 6H); 13C δ 15.9 [788]; 25.1 [40];
36.4 [116]; 87.5 [900]; 110.3 [204]; 122.7 [22]; 128.4; 129.0;
132.4 [13]; 119Sn δ -242.1. Anal. Calcd for C53H40Sn2: C, 69.63;
H, 4.41; Sn, 25.96. Found: C, 68.07; H, 4.33; Sn, 26.31.
1,4-Bis(tr ip r op -1-yn ylsta n n yl)ben zen e, 19: mp >250 °C;
OM0202468
(20) Cosier, J .; Glazer, A. M. J . Appl. Crystallogr. 1986, 19, 105.
(21) Otwinowski, Z.; Minor, W. Methods Enzymol. 1997, 276, 307-
326.
(22) Altomare, A.; Cascarano, G.; Giacovazzo, G.; Guagliardi, A.;
Burla, M. C.; Polidori, G.; Camalli, M. J . Appl. Crystallogr. 1994, 27,
1045-1050.
(23) Larson, A. C. Crystallographic Computing; Ahmed, F. R., Ed.;
Munksgaard: Copenhagen, 1970; p 291.
(24) Carruthers, J . R.; Watkin, D. J . Acta Crystallogr. 1979, A35,
698.
(25) Watkin, D. J .; Prout, C. K.; Carruthers, R. J .; Betteridge, P.
CRYSTALS; Chemical Crystallography Laboratory; University of
Oxford, UK, 1996. Watkin, D. J .; Prout, C. K.; Pearce, L. J . CAMERON;
Chemical Crystallography Laboratory; University of Oxford: UK, 1996.
1
47% yield; H δ 1.85 (s, 18H); 7.62 (s, 4H [13.2, 39.5]); 13C δ
5.5 [9]; 76.0; 108.9; 128.5; 136.1; 119Sn δ -288.03. Anal. Calcd
for C24H22Sn2: C, 52.62; H, 4.05; Sn, 43.33. Found: C, 52.08;
H, 4.13; Sn, 42.37.