Synthesis, structures and reactions of novel 9,10-dihydro-9,10- distannaanthracenes

Article abstract of DOI:10.1002/ejic.200300382

A method for the synthesis of 9,10-dihydro-9,10-distannaanthracenes has been improved and applied to the synthesis of novel unsymmetrical 9,10-dihydro-9,10-distannaanthracenes. The first 9,9,10,10-tetrahalo-9,10- dihydro-9,10-distannaanthracenes were successfully synthesized by halogenation of 9,9,10,10-tetrakis(p-methoxyphenyl)-9,10-dihydro-9,10-distannaanthracene. The structures of the newly obtained 9,10-dihydro-9,10-distannaanthracenes were determined by X-ray analysis. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300382

FULL PAPER
Synthesis, Structures and Reactions of Novel 9,10-Dihydro-9,10-
distannaanthracenes
Masaichi Saito,*[a] Natsumi Henzan,[a] Minehiko Nitta,[a] and Michikazu Yoshioka[a]
Keywords: Halogenation / Synthesis design / Tin
A method for the synthesis of 9,10-dihydro-9,10-distan-
dihydro-9,10-distannaanthracene. The structures of the
naanthracenes has been improved and applied to the syn- newly obtained 9,10-dihydro-9,10-distannaanthracenes were
thesis of novel unsymmetrical 9,10-dihydro-9,10-distan-
naanthracenes. The first 9,9,10,10-tetrahalo-9,10-dihydro-
9,10-distannaanthracenes were successfully synthesized by
halogenation of 9,9,10,10-tetrakis(p-methoxyphenyl)-9,10-
determined by X-ray analysis.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
ilaanthracenes. 9,9,10,10-Tetrahalogenated 9,10-dihydro-
9,10-distannaanthracenes are expected to be good precur-
sors for reactive tin-containing species having a 9,10-distan-
naanthracene skeleton. However, no report on such halog-
enated derivatives has appeared.
We report herein an improved method for the synthesis
of aryl-substituted and unsymmetrical substituted 9,10-di-
hydro-9,10-distannaanthracenes. Halogenation of 9,9,10,10-
tetrakis(p-methoxyphenyl)-9,10-dihydro-9,10-
distannaanthracene to give the first 9,9,10,10-tetrahalo-
9,10-dihydro-9,10-distannaanthracenes is also reported.
The structures of the newly obtained 9,10-dihydro-9,10-dis-
tannaanthracenes are discussed.
Since the first synthesis of 9,9,10,10-tetraphenyl-9,10-di-
hydro-9,10-disilaanthracene,[1] studies of the synthesis,
structures, and reactions of 9,10-dihydro-9,10-disilaanthra-
cene have been developed.[2] The corresponding germanium
analogs, 9,10-dihydro-9,10-digermaanthracenes, have also
been synthesized and characterized.[3] One of the interesting
features of 9,10-dihydro-9,10-dimetallaanthracenes is the
conformations of their central six-membered rings which
are dependent on substituents on the metal.[4Ϫ7] Although
a few 9,10-dihydroanthracenes having a tin atom at the 10-
position have been reported,[4,8] only one report on the
9,10-dihydro-9,10-distannaanthracene has appeared, but
without synthetic or structural details.[9] During the course
of our studies on tin-containing compounds with unique
structures, we have already reported the first syntheses and
structures of 9,9,10,10-tetramethyl- and 9,9,10,10-tetra-tert-
Results and Discussion
Improved Method for the Synthesis of 9,10-Dihydro-9,10-
distannaanthracenes
butyl-9,10-dihydro-9,10-distannaanthracenes.[7,10]
The
A
previous publication reported the synthesis of
tetramethyl derivative has a butterfly conformation, while
the tetra-tert-butyl derivative has a planar structure. The
dependence of conformation on substituents prompted us
to investigate some other 9,10-dihydro-9,10-distan-
naanthracenes having aryl groups and those with unsym-
metrical structures. The utility of 9,10-dihydro-9,10-dimet-
allaanthracene derivatives as potential precursors for metal-
containing reactive species is also of interest. Recently, fas-
cinating silicon-containing reactive species such as a bis(si-
lyl anion)[11] and a relatively stable silyl radical[6] have been
reported to be derived from 9,10-dihydro-9,10-dis-
9,9,10,10-tetramethyl-9,10-dihydro-9,10-
distannaanthracene (1) from the reaction of bis(o-bromo-
phenyl)dimethylstannane (2) and dichlorodimethylstannane
with magnesium in the presence of a catalytic amount of
copper() cyanide in 25% yield.[7] By using tert-butyllithium
for the lithiation of 2 in THF at Ϫ78 °C, the yield of 1 was
increased to 51% (Scheme 1).
Introduction of p-methoxyphenyl groups on the tin was
examined using tert-butyllithium. Bis(o-bromophenyl)bis(p-
methoxylphenyl)stannane (3) was synthesized by the reac-
tion of (2-bromophenyl)lithium with bis(p-methoxyphenyl)-
dichlorostannane[12] in 48% yield. Lithiation of 3 using tert-
butyllithium and subsequent reaction with bis(p-methoxy-
phenyl)dichlorostannane gave the 9,9,10,10-tetrakis(p-
methoxyphenyl)-substituted compound 4 in 46% yield
(Scheme 1).
[a]
Department of Chemistry, Faculty of Science, Saitama
University,
Shimo-okubo, Sakura-ku, Saitama City, Saitama, 338Ϫ8570
Japan
E-mail: masaichi@chem.saitama-u.ac.jp
Eur. J. Inorg. Chem. 2004, 743Ϫ748
DOI: 10.1002/ejic.200300382
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
743

M. Saito, N. Henzan, M. Nitta, M. Yoshioka
FULL PAPER
Scheme 1
Synthesis of Unsymmetrically-Substituted 9,10-Dihydro-
9,10-distannaanthracenes
good precursors for reactive tin-containing species such as
9,10-distannaanthracene.
This improved method can be applied to the synthesis of
unsymmetrically-substituted
9,10-dihydro-9,10-distan-
naanthracenes. Thus, lithiation of 2 and 3 with tert-butyl-
lithium in THF at Ϫ78 °C and subsequent treatment with
di-tert-butyldichlorostannane and dichlorodimethylstan-
nane gave the 9,9-di-tert-butyl-10,10-dimethyl-substituted
and 9,9-bis(p-methoxyphenyl)-10,10-dimethyl-substituted
compounds 5 and 6 in yields of 19 and 14%, respectively
(Scheme 1). The structures of 5 and 6 were determined
Scheme 2
1
using H and 13C NMR spectroscopy and elemental analy-
sis.
Halogenation of 9,10-Dihydro-9,10-distannaanthracenes
In order to prepare further functionalized 9,10-dihydro-
9,10-distannaanthracenes, the halogenations of the tetra-
tert-butyl-substituted
9,10-dihydro-9,10-distannaanthra-
cene 7[7] and the 9,9,10,10-tetrakis(p-methoxyphenyl)-sub-
stituted 9,10-dihydro-9,10-distannaanthracene 4 were inves-
tigated. Reaction of 7 with bromine (1 equiv.) gave the di-
bromide 8 (77%) through the cleavage of a tinϪphenyl bond
because the ease of cleavage of the SnϪC bond is in the
order of SnϪaromatic Ͼ Ϫvinyl Ͼ Ϫalkyl (Scheme 2).[13]
Conversely, chlorination of 4 using acetyl chloride and
aluminum chloride[14] gave 9,9,10,10-tetrachloro-9,10-di-
hydro-9,10-distannaanthracene (9), reflecting the ease of
cleavage of an SnϪp-methoxyphenyl bond (Scheme 3). The
p-methoxyphenyl group on tin is easily substituted by a hal-
ogen.[14] Reaction of 4 with iodine gave the tetraiodide 10
Scheme 3
X-ray Crystallographic Structures of the Newly Obtained
9,10-Dihydro-9,10-distannaanthracenes 4, 6, and 10
The X-ray crystallographic analyses were carried out at
(Scheme 3). These haloganated 9,10-dihydro-9,10-distan- room temperature. The molecular structures of 4, 6, and 10
naanthracenes, the first examples of a 9,9,10,10-tetrahalo- with selected bond lengths and angles are shown in Figures
9,10-dihydro-9,10-distannaanthracene, are expected to be 1, 2, and 3, respectively. The central six-membered ring of
744
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Eur. J. Inorg. Chem. 2004, 743Ϫ748

Novel 9,10-Dihydro-9,10-distannaanthracenes
FULL PAPER
6 adopts a boat conformation and hence the tricyclic frame-
work has a butterfly conformation with a dihedral angle
of 156° as observed in the 9,9,10,10-tetramethyl derivative
(143°).[7] Although 9,9,10,10-tetraphenyl-9,10-dihydro-9,10-
disilaanthracene has a planar structure,[15] the central six-
membered ring of 4 has a boat conformation with a di-
hedral angle of 149° due to the SnϪC6H4OMe-p bonds be-
ing longer than the SiϪPh bonds in the tetraphenyl com-
pound so that the p-methoxyphenyl group can be orientated
in a pseudoaxial position. The tetra-iodo derivative 10 has
a planar structure, as observed in the 9,9,10,10-tetra-tert-
butyl derivative,[7] probably due to the steric bulk of the
iodine atom.
Figure 1. ORTEP drawing of 4 with thermal ellipsoids plots (40%
˚
probability for non-hydrogen atoms); selected bond lengths [A] and
angles (deg): Sn(1)ϪC(13) 2.127(3), Sn(1)ϪC(20) 2.127(3),
Sn(2)ϪC(27) 2.135(3), Sn(2)ϪC(34) 2.130(3); C(1)ϪSn(1)ϪC(12)
108.90(12), C(6)ϪSn(2)ϪC(7) 109.07(12), C(13)ϪSn(1)ϪC(20)
111.22(13), C(7)ϪSn(2)ϪC(34) 109.00(13)
Figure 3. ORTEP drawing of 10 with thermal ellipsoids plots (40%
˚
probability for non-hydrogen atoms); selected bond lengths [A] and
angles (deg): Sn(1)ϪI(1) 2.6812(8), Sn(1)ϪI(2) 2.6795(8),
Sn(1)ϪC(1) 2.129(7), Sn(1)ϪC(2) 2.124(8); C(1)ϪSn(1)ϪC(2)
114.8(3), I(1)ϪSn(1)ϪI(2) 104.76(3)
Conclusion
A novel method for the synthesis of 9,10-dihydro-9,10-
distannanthracenes has been developed and novel 9,10-di-
hydro-9,10-distannanthracenes having unsymmetrical struc-
tures have been synthesized. Halogenation of 9,9,10,10-
tetrakis(p-methoxyphenyl)-9,10-dihydro-9,10-distanna-
anthracene gave the first 9,9,10,10-tetrahalo-9,10-dihydro-
9,10-distannaanthracenes. Although the 9,10-dihydro-9,10-
distannanthracenes having p-methoxyphenyl groups on the
tin have a butterfly conformation, the 9,9,10,10-tetraiodo
derivative has a planar structure for steric reasons. Further
investigations on the synthesis of reactive tin-containing
species having a 9,10-distannaanthracene skeleton from
9,9,10,10-tetrahalo derivatives are currently in progress.
Figure 2. ORTEP drawing of 6 with thermal ellipsoids plots (40%
˚
probability for non-hydrogen atoms); selected bond lengths [A] and
Experimental Section
angles (deg): Sn(1)ϪC(13) 2.137(3), Sn(1)ϪC(20) 2.146(4),
Sn(2)ϪC(27) 2.145(5), Sn(2)ϪC(28) 2.128(5); C(1)ϪSn(1)ϪC(12)
110.18(13), C(6)ϪSn(2)ϪC(7) 108.63(13), C(13)ϪSn(1)ϪC(20)
108.19(13), C(7)ϪSn(2)ϪC(27) 112.3(2)
General Procedure: All reactions were carried out under argon.
THF and diethyl ether used in the syntheses were distilled from
Eur. J. Inorg. Chem. 2004, 743Ϫ748
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M. Saito, N. Henzan, M. Nitta, M. Yoshioka
FULL PAPER
sodium benzophenone ketyl under an argon atmosphere before use.
Magnesium (turnings) was purchased from Wako Pure Chemical
Industries, Ltd. 1H (400 MHz), 13C NMR (101 MHz) and 119Sn
to room temperature. The resultant mixture was extracted with di-
ethyl ether and the organic layer was washed with aqueous NH4Cl.
After removal of volatile components, the residue was subjected to
NMR (149 MHz) spectra were recorded on a Bruker AM-400 or WCC (SiO2, hexane/dichloromethane, 1:4) followed by recrystalli-
an ARX-400 spectrometer in CDCl3 with tetramethylsilane as an zation from hexane and dichloromethane to give 9,9,10,10-tetra-
internal standard. Although nJ(SnϪ13C) couplings were observed
in the 13C NMR spectra as satellite signals, most of the
nJ(119SnϪ13C) and nJ(117SnϪ13C) values could not be separately
kis(p-methoxyphenyl)-9,10-dihydro-9,10-distannaanthracene
(4)
(0.584 g, 46%). 4: M.p. 221Ϫ222 °C (recrystallization from hexane/
1
dichloromethane). H NMR: δ ϭ 3.77 (s, 12 H), 6.79Ϫ6.83 (m, 8
estimated because of broadening. The multiplicities of signals in the H), 7.28Ϫ7.29 (m, 4 H), 7.34Ϫ7.36 (m, 8 H), 7.57Ϫ7.60 (m, 4 H).
13C NMR spectra given in parentheses were deduced from DEPT
spectra. Wet column chromatography (WCC) was carried out by
using Merck Kieselgel 60 (SiO2). All melting points were deter-
13C NMR: δ ϭ 54.9 (q), 114.3 (d), 128.6 [s, 1J(SnϪC) ϭ 522,
546 Hz], 128.8 [d, J(SnϪC) ϭ 49 Hz], 137.3 [d, J(SnϪC) ϭ 45,
55 Hz], 138.4 [d, J(SnϪC) ϭ 44 Hz], 150.8 [s, 1J(SnϪC) ϭ 520,
mined on a Mitamura Riken Kogyo MEL-TEMP apparatus and 544, 2J(SnϪC) ϭ 52 Hz], 160.3 (s). 119Sn NMR: δ ϭ Ϫ173.6
are uncorrected. Elemental analyses were carried out at the Micro-
analytical Laboratory of the Chemical Analysis Center, Saitama
University. Data for the X-ray crystallographic analyses were col-
lected on Mac Science Xdip or MXC18 K diffractometers with
[3J(SnϪSn) ϭ 761 Hz] ppm. C40H36O4Sn2 (818.16): calcd. C 58.72,
H 4.44; found C 58.63, H 4.29.
Preparation of 9,9-Di-tert-butyl-10,10-dimethyl-9,10-dihydro-9,10-
distannaanthracene (5): To a THF (10 mL) solution of 2 (240 mg,
˚
Mo-Kα radiation (λ ϭ 0.71073 A) and the structures were solved
0.52 mmol) was added tBuLi (1.60
 in pentane; 1.30 mL,
by direct methods.
2.08 mmol) at Ϫ78 °C and the resultant solution was stirred at this
temperature for 30 min. To the reaction mixture was added a THF
(5 mL) solution of di-tert-butyldichlorostannane (160 mg,
0.50 mmol) at the same temperature. After stirring for 2 h at Ϫ78
°C, the reaction mixture was gradually allowed to warm to room
temperature. The resultant mixture was extracted with diethyl ether
and the organic layer was washed with aqueous NH4Cl. After re-
moval of volatile components, the residue was subjected to WCC
(SiO2, hexane/ethyl acetate, 100:1) to afford 9,9-di-tert-butyl-10,10-
dimethyl-9,10-dihydro-9,10-distannaanthracene (5) (52 mg, 19%).
5: M.p. 77Ϫ79 °C (recrystallization from hexane/methanol). 1H
NMR: δ ϭ 0.36 [s, 6 H, 2J(SnϪH) ϭ 52, 55 Hz], 1.30 [s, 18 H,
3J(SnϪH) ϭ 63, 65 Hz], 7.27Ϫ7.30 (m, 4 H), 7.54Ϫ7.56 (m, 4 H).
13C NMR: δ ϭ Ϫ7.7 [q, 1J(SnϪC) ϭ 329, 345 Hz], 29.9 [s,
1J(SnϪC) ϭ 365, 382 Hz], 31.5 (q), 127.6 (d), 128.1 (d), 136.3 [d,
J(SnϪC) ϭ 42, 48 Hz], 137.4 [d, J(SnϪC) ϭ 42, 54 Hz], 152.0 [s,
Improved Synthesis of 9,9,10,10-Tetramethyl-9,10-dihydro-9,10-dis-
tannaanthracene (1): To a THF (10 mL) solution of bis(o-bromo-
phenyl)dimethylstannnane[7] (2) (232 mg, 0.50 mmol) was added
tBuLi (1.60  in pentane; 1.25 mL, 2.00 mmol) at Ϫ78 °C and the
resultant solution was stirred at this temperature for 1 h. After ad-
dition of a THF (5 mL) solution of dichlorodimethylstannane
(110 mg, 0.50 mmol) at the same temperature, the reaction mixture
was allowed to warm to room temperature. The resultant mixture
was extracted with diethyl ether and the organic layer was washed
with aqueous NH4Cl. After removal of volatile components, the
residue was subjected to WCC (SiO2, hexane/ethyl acetate, 20:1) to
afford
9,9,10,10-tetramethyl-9,10-dihydro-9,10-distannaanthra-
cene[7] (1) (116 mg, 51%).
Preparation of Bis(o-bromophenyl)bis(p-methoxylphenyl)stannane
(3): To a solution of butyllithium (1.56  in hexane; 6.24 mL,
4.00 mmol) in a mixture of THF (10 mL) and diethyl ether (10 mL)
was added 1,2-dibromobenzene (0.72 mL, 5.97 mmol) at Ϫ110 °C
and the resultant solution was stirred at this temperature for 1.5 h.
Subsequently, bis(p-methoxyphenyl)dichlorostannane[12] (1.304 g,
3.23 mmol) in THF (5 mL) and diethyl ether (5 mL) was added
at Ϫ110 °C. The reaction mixture was allowed to warm to room
temperature. The resultant mixture was extracted with diethyl ether
and the organic layer was washed with aqueous NH4Cl. After re-
moval of volatile components, the residue was subjected to WCC
(SiO2, hexane/dichloromethane, 1:3) followed by recrystallization
from dichloromethane and methanol to give bis(o-bromophe-
nyl)bis(p-methoxylphenyl)stannane (3) (0.926 g, 48%). 3: M.p.
142Ϫ145 °C (recrystallization from dichloromethane/methanol).
1H NMR: δ ϭ 3.82 (s, 6 H), 6.94Ϫ6.99 (m, 4 H), 7.25Ϫ7.27 (m, 4
H), 7.38Ϫ7.40 (m, 2 H), 7.52Ϫ7.68 (m, 6 H). 13C NMR: δ ϭ 55.0
(q), 114.4 [d, J(SnϪC) ϭ 61 Hz), 126.9 [d, J(SnϪC) ϭ 47 Hz),
128.4 (s), 130.9 (d), 132.1 [d, J(SnϪC) ϭ 31 Hz), 132.5 [s,
J(SnϪC) ϭ 14 Hz], 138.6 [d, J(SnϪC) ϭ 46 Hz], 139.3 [d,
J(SnϪC) ϭ 36 Hz), 144.5 (s), 160.4 (s). 119Sn NMR: δ ϭ Ϫ116.5
ppm. C26H22Br2O2Sn (644.98): calcd. C 48.42, H 3.44; found C
48.54, H 3.35.
2
1
1J(SnϪC) ϭ 362, 379, J(SnϪC) ϭ 53 Hz], 153.4 [s, J(SnϪC) ϭ
500, 523, 2J(SnϪC)
ϭ δ ϭ Ϫ156.3
35 Hz]. 119Sn NMR:
[3J(SnϪSn) ϭ 497, 546 Hz], Ϫ121.1 [3J(SnϪSn) ϭ 497, 546 Hz]
ppm. C22H32Sn2 (533.94): calcd. C 49.49, H 6.04; found C 49.96,
H 6.06.
Preparation of 9,9-Bis(p-methoxyphenyl)-10,10-dimethyl-9,10-di-
hydro-9,10-distannaanthracene (6): To a THF (5 mL) solution of 3
(196 mg, 0.30 mmol) was added tBuLi (1.60  in pentane; 0.75 mL,
1.20 mmol) at Ϫ78 °C and the resultant solution was stirred at this
temperature for 1 h. To the reaction mixture was added a THF
(5 mL) solution of dichlorodimethylstannane (74 mg, 0.30 mmol)
at the same temperature. After stirring for 1 h at Ϫ78 °C, the reac-
tion mixture was gradually allowed to warm to room temperature.
The resultant mixture was extracted with diethyl ether and the or-
ganic layer was washed with aqueous NH4Cl. After removal of
volatile components, the residue was subjected to WCC (SiO2, hex-
ane/ethyl acetate, 6:1) to afford 9,9-bis(p-methoxyphenyl)-10,10-di-
methyl-9,10-dihydro-9,10-distannaanthracene (6) (27 mg, 14%). 6:
M.p. 115Ϫ118 °C (recrystallization from hexane/dichloromethane).
2
1H NMR: δ ϭ 0.32 [s, 6 H, J(SnϪH) ϭ 54, 56 Hz], 3.80 (s, 6 H),
6.93 (d, J ϭ 9 Hz, 4 H), 7.24Ϫ7.28 (m, 2 H), 7.30Ϫ7.34 (m, 2 H),
Preparation of 9,9,10,10-Tetrakis(p-methoxyphenyl)-9,10-dihydro-
7.38Ϫ7.50 (m, 4 H), 7.53Ϫ7.65 (m, 4 H). 13C NMR: δ ϭ Ϫ8.5 [q,
9,10-distannaanthracene (4): To a THF (10 mL) solution of 3 1J(SnϪC) ϭ 344 Hz], 55.0 (q), 114.5 [d, J(SnϪC) ϭ 55 Hz], 128.3
(1.006 g, 1.56 mmol) was added tBuLi (1.6  in pentane; 3.0 mL,
4.8 mmol) at Ϫ78 °C and the resultant solution was stirred at this
(d), 128.6 (d), 128.9 (s), 136.1 [d, J(SnϪC) ϭ 46, 56 Hz], 136.9 [d,
J(SnϪC) ϭ 55 Hz], 138.4 [d, J(SnϪC) ϭ 44 Hz], 150.0 (s), 152.7
temperature for 20 min. After addition of a THF (5 mL) solution (s), 160.5 (s). 119Sn NMR: δ ϭ Ϫ171.6 [3J(SnϪSn) ϭ 727, 796 Hz],
of bis(p-methoxyphenyl)dichlorostannane[12] (0.684 g, 1.69 mmol)
Ϫ116.5 [3J(SnϪSn) ϭ 727, 796 Hz] ppm. C28H28O2Sn2 (633.96):
at the same temperature, the reaction mixture was allowed to warm
calcd. C 53.05, H 4.45; found C 53.32, H 4.38.
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Novel 9,10-Dihydro-9,10-distannaanthracenes
FULL PAPER
Reaction of 9,9,10,10-Tetra-tert-butyl-9,10-dihydro-9,10-distan-
naanthracene (7) with Bromine: To a carbon tetrachloride (15 mL)
solution of 7 (162 mg, 0.26 mmol) was added a carbon tetra-
diffractometer using graphite-monochromated Mo-Kα radiation
˚
(λ ϭ 0.71073 A). The structure was solved by direct methods using
SIR[16] and refined by full-matrix least-squares procedures
chloride (5 mL) solution of bromine (42 mg, 0.26 mmol) at room (SHELXL-97)[17] on F2 for all reflections (5432 reflections) for 290
temperature. After removal of the solvent, the residue was recrys-
tallized from dichloromethane and methanol to give [2- (bromodi-
variable parameters. R1(wR2)
GOF ϭ 1.060.
ϭ 0.039 (0.090) for all data,
tert-butylstannyl)](2-bromophenyl)di-tert-butylstannane
(133 mg, 77%). 8: M.p. 182Ϫ184 °C (recrystallization from di-
chloromethane/methanol). 1H NMR:
1.26 [s, 18 H,
(8)
Crystal and Experimental Data at 298 K for 10: C6H4I2Sn, M ϭ
448.596, crystal size 0.40 ϫ 0.40 ϫ 0.20 mm, triclinic, a ϭ 7.407(5),
δ
ϭ
˚
3J(SnϪH) ϭ 81, 84 Hz], 1.36 [br. s, 18 H, 3J(SnϪH) ϭ 68 Hz],
7.04Ϫ7.17 (m, 3 H), 7.20Ϫ7.24 (m, 1 H), 7.31Ϫ7.35 (m, 1 H),
7.50Ϫ7.55 (m, 1 H), 7.73Ϫ7.75 (m, 1 H). 13C NMR: δ ϭ 30.8 (q),
31.6 (br. q), 35.9 [s, 1J(SnϪC) ϭ 360, 377 Hz], 125.8 [d, J(SnϪC) ϭ
34 Hz], 126.4 [d, J(SnϪC) ϭ 11, 62 Hz], 127.5 [d, J(SnϪC) ϭ 15,
40 Hz], 129.0 (d), 131.7 (s), 131.8 (d), 136.8 [d, J(SnϪC) ϭ 48,
83 Hz], 139.2 [d, J(SnϪC) ϭ 23 Hz], 141.0 [d, J(SnϪC) ϭ 38,
61 Hz], 151.4 [s, J(SnϪC) ϭ 43 Hz], 151.9 (s), 153.3 [s, J(SnϪC) ϭ
50 Hz]. 119Sn NMR: δ ϭ Ϫ78.5 (br.), 3.9 ppm. C28H44Br2Sn2
(777.92): calcd. C 43.23, H 5.70; found C 43.45, H 5.72.
b ϭ 8.042(4), c ϭ 9.203(7) A, α ϭ 102.42(5), β ϭ 108.29(5), γ ϭ
3
104.52(6)°, V ϭ 477.4(5) A , D ϭ 3.121 Mg·mϪ3, µ(Mo-Kα) ϭ
˚
9.066 mmϪ1, Z ϭ 2, space group P1. Data were collected on a Mac
¯
Science MXC18 K diffractometer using graphite-monochromated
˚
Mo-Kα radiation (λ ϭ 0.71073 A). The structure was solved by
direct methods using SIR[16] and refined by full-matrix least-
squares procedures (SHELXL-97)[17] on F2 for all reflections (2175
reflections) for 83 variable parameters. R1(wR2) ϭ 0.052 (0.145) for
all data, GOF ϭ 1.041.
CCDC-212959 (4), -212958 (6) -213182 (10) contain the sup-
plementary crystallographic data for these compounds. These data
can be obtained free of charge at www.ccdc.cam.ac.uk/conts/re-
trieving.html (or from the Cambridge Crystallographic Data
Center, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.)
ϩ44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk).
Preparation of 9,9,10,10-Tetrachloro-9,10-dihydro-9,10-distan-
naanthracene (9): To a toluene (5 mL) solution of 4 (183 mg,
0.22 mmol) was added acetyl chloride (0.063 mL, 0.84 mmol) in the
presence of a catalytic amount of aluminum trichloride at 0 °C.
After separation of insoluble materials in dichloromethane by fil-
tration, the residue was crystallized from chloroform and dichloro-
methane to afford 9,9,10,10-tetrachloro-9,10-dihydro-9,10-distan-
naanthracene (9) (24 mg, 18%). 6: M.p. 285Ϫ288 °C (decomp.)
(recrystallization from dichloromethane/chloroform). 1H NMR:
δ ϭ 7.63Ϫ7.69 (m, 4 H), 7.74Ϫ7.94 (m, 4 H). 13C NMR: δ ϭ 133.1
[d, J(SnϪC) ϭ 92 Hz, Cβ], 137.1 [d, J(SnϪC) ϭ 84, 103 Hz, Cα],
152.4 (s, Cipso) ppm. C12H8Cl4Sn2 (531.4): calcd. C 27.12, H 1.52;
found C 27.28, H 1.42.
Acknowledgments
This work was partially supported by Grant-in-Aids for the En-
couragement of Young Scientists, Nos. 10740288 (M. S.) and
13740349 (M. S.) from the Ministry of Education, Science, Sports
and Culture, Japan and from the Japan Society for the promotion
of Science, respectively. M. Saito also acknowledges a research
grant from the Toray Science Foundation.
Preparation
of
9,9,10,10-Tetraiodo-9,10-dihydro-9,10-distan-
naanthracene (10): A dichloromethane (50 mL) solution of iodine
(700 mg, 2.76 mmol) was added to a dichloromethane (10 mL)
solution of 4 (566 mg, 0.69 mmol). The mixture was heated to re-
flux for 1 day. After separation of insoluble materials in diethyl
ether by filtration, the residue was crystallized from dichlorometh-
ane to afford 9,9,10,10-tetraiodo-9,10-dihydro-9,10-distan-
naanthracene (10) (316 mg, 51%). 10: M.p. 278Ϫ280 °C (recrystalli-
zation from dichloromethane). 1H NMR: δ ϭ 7.52Ϫ7.55 (m, 4 H),
7.63Ϫ7.83 (m, 4 H). 13C NMR: δ ϭ 132.2 [d, J(SnϪC) ϭ 14,
66 Hz, Cβ], 136.9 [d, J(SnϪC) ϭ 46, 76 Hz, Cα], 148.3 (s, Cipso).
119Sn NMR: δ ϭ 189.1 ppm. C12H8I4Sn2 (897.2): calcd. C 16.06,
H 0.90; found C 16.16, H 0.77.
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For a review, see: T. J. Barton, Comprehensive Organometallic
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Crystal and Experimental Data at 298 K for 4: C40H36O4Sn2, M ϭ
818.104, crystal size 0.30 ϫ 0.30 ϫ 0.20 mm, monoclinic, a ϭ
See references cited in ref.[4]
[5]
[6]
˚
18.191(5), b ϭ 11.400(2), c ϭ 19.522(10) A, β ϭ 118.23(6) °, V ϭ
S. Kyushin, T. Shinnai, T. Kubota, H. Matsumoto, Organomet-
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3
3572(2) A , D ϭ 1.521 Mg·mϪ3, µ(Mo-Kα) ϭ 1.437 mmϪ1, Z ϭ 4,
˚
[7]
space group P21/c. Data were collected on a Mac Science
MXC18 K diffractometer by using graphite-monochromated Mo-
[8]
[9]
˚
Kα radiation (λ ϭ 0.71073 A). The structure was solved by direct
methods using SIR[16] and refined by full-matrix least-squares pro-
cedures (SHELXL-97)[17] on F2 for all reflections (7777 reflections)
for 416 variable parameters. R1(wR2) ϭ 0.037 (0.091) for all data,
GOF ϭ 1.158.
[10]
9,10-Distannatriptycene has been synthesized and charac-
terized, see: M. A. Dam, O. S. Akkerman, F. J. J. de Kanter,
F. Bickelhaupt, N. Veldman, A. L. Spek, Chem. Eur. J. 1996,
2, 1139Ϫ1142.
Crystal and Experimental Data at 298 K for 6: C28H28O2Sn2, M ϭ
633.91, crystal size 0.30 ϫ 0.30 ϫ 0.10 mm, monoclinic, a ϭ
[11] [11a]
W. Ando, K. Hatano, R. Urisaka, Organometallics 1995,
14, 3625Ϫ3627. [11b] K. Hatano, K. Morihashi, O. Kikuchi, W.
Ando, Chem. Lett. 1997, 293Ϫ294.
˚
17.2610(5), b ϭ 9.4070(3), c ϭ 28.0101(6) A, β ϭ 144.904(1)°, V ϭ
3
2615.0(1) A , D ϭ 1.610 Mg·mϪ3, µ(Mo-Kα) ϭ 1.931 mmϪ1, Z ϭ 4,
˚
[12]
B. N. Biddle, J. S. Gray, A. J. Crowe, Appl. Organomet. Chem.
1987, 1, 261Ϫ265.
space group P21/c. Data were collected on a Mac Science DIP3000
Eur. J. Inorg. Chem. 2004, 743Ϫ748
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
747

M. Saito, N. Henzan, M. Nitta, M. Yoshioka
FULL PAPER
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[16]
[17]
W. P. Neumann, The Organic Chemistry of Tin, John
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many, 1997.
[13b]
R. C. Poller, The Chemis-
[13c]
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[14]
[15]
Received June 19, 2003
Early View Article
Published Online December 19, 2003
748
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 743Ϫ748