Synthesis and structures of polychalcogenadistannabicyclo[k.l.m]alkanes

Article abstract of DOI:10.1016/j.jorganchem.2007.02.004

Reaction of steric encumbered trichlorostannane with disodium sulfide or dilithium selenide gave 2,4-dimercapto-1,3,2,4-dithiadistannetane or tetraselenadistannabicyclo[2.1.1]hexane, respectively. Reactions of steric encumbered trihydrostannane with elemental chalcogens gave pentachalcogenadistannabicyclo[k.1.1]heptanes (k = 2 and 3). The two bridgehead tin atoms of the first polychalcogenadistannabicyclo[k.l.m]alkanes are concluded to have no significant bonding interaction, judging from the longer bond distances than those of the normal tin-tin single bonds.

Full text of DOI:10.1016/j.jorganchem.2007.02.004

Journal of Organometallic Chemistry 692 (2007) 2729–2735
www.elsevier.com/locate/jorganchem
Synthesis and structures of
polychalcogenadistannabicyclo[k.l.m]alkanes
*
Masaichi Saito , Hizuru Hashimoto, Tomoyuki Tajima, Masatoshi Ikeda
Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama-city,
Saitama 338-8570, Japan
Received 17 November 2006; received in revised form 6 February 2007; accepted 6 February 2007
Available online 16 February 2007
Abstract
Reaction of steric encumbered trichlorostannane with disodium sulfide or dilithium selenide gave 2,4-dimercapto-1,3,2,4-dithiadist-
annetane or tetraselenadistannabicyclo[2.1.1]hexane, respectively. Reactions of steric encumbered trihydrostannane with elemental
chalcogens gave pentachalcogenadistannabicyclo[k.1.1]heptanes (k = 2 and 3). The two bridgehead tin atoms of the first polychalcoge-
nadistannabicyclo[k.l.m]alkanes are concluded to have no significant bonding interaction, judging from the longer bond distances than
those of the normal tin–tin single bonds.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Polychalcogenadistannabicyclo[k.l.m]alkanes; Tin; Sulfur; Selenium
1. Introduction
M = Si, Ge; Ch = S, Se) by the dechalcogenation of the cor-
responding polythia- and polyselena-dimetallabicy-
clo[k.l.m]alkanes 2 (R = tris(trimethylsilyl)methyl; M = Si,
Ge; Ch = S, Se) (Scheme 1) [11]. As for tin analogues, how-
ever, neither trichalcogenadistannabicyclo[1.1.1]pentane
derivative 1 (M = Sn) nor polychalcogenadistannabicy-
clo[k.l.m]alkanes 2 (M = Sn) has been reported [12]. We
report herein the synthesis of novel tin-containing cage-like
polychalcogenides, polythia- and polyselena-distannabicy-
clo[k.l.m]alkanes 2 and their structural properties.
Over the past decade much attention has been paid to the
chemistry of cage-like compounds containing heavier
Groups 14 and 16 elements from the standpoints of their
unique structure and reactivity [1,2]. Some cage compounds
such as double decker- and adamantane-type compounds of
heavier Groups 14 and 16 elements have been synthesized
and characterized [3–8]. Among cage-like compounds, the
nature of the bridgehead bond of bicyclo[1.1.1]pentanes
has been of considerable interest. According to theoretical
studies, the type of H2M2Ch3 [1.1.1]propellanes 1 (R = H;
M = Si, Ge, Sn; Ch = O) is predicted to have a short non-
bonded distance between the two bridgehead Group 14
atoms [9,10]. Although no reports on the synthesis of triox-
adimetallabicyclo[1.1.1]pentanes of heavier Group 14 ele-
ments have so far appeared, trithia- and triselena-
derivatives have been relatively well-investigated. Ando
et al. reported the synthesis of trithia- and triselenadimetal-
labicyclo[1.1.1]pentanes 1 (R = tris(trimethylsilyl)methyl;
2. Results and discussion
2.1. Synthesis of aryltrichloro- 4 and aryltrihydrostannanes 3
Since some silicon derivatives of polythiabicy-
clo[1.1.1]pentane are moisture-sensitive even by the intro-
duction of a bulky tris(trimethylsilyl)methyl group on the
silicon atom [11], we chose a bulky m-terphenyl ligand,
2,6-bis(2,4,6-triisopropylphenyl)phenyl (denoted as Ar
hereafter) group as an efficient steric protection group,
which has been utilized for the kinetic stabilization of
highly reactive species having a heavier Group 14 elements
*
Corresponding author. Tel.: +81 48 858 9029; fax: +81 48 858 3698.
E-mail address: masaichi@chem.saitama-u.ac.jp (M. Saito).
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.02.004

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M. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 2729–2735
Scheme 1.
[13,14]. The starting compound, aryltrichlorostannane 4,
was prepared by the reaction of in situ-generated chlorost-
annylene 5 [15] with carbon tetrachloride [16] (Scheme 2) in
45% yield. Reduction of aryltrichlorostannane 4 with
LiAlH4 in THF gave aryltrihydrostannane 3 in 83% yield.
Scheme 3.
main fraction consisted of dimeric products, judging from
its retention time of gel permeation chromatography. The
119Sn NMR spectrum of the dimeric fraction in CDCl3
showed signals at À31.7 (6), À30.0, À9.6, À9.2, À7.2,
29.8 (8), 49.2 and 110.0 ppm. Although the mixture might
contain some polysulfides, their separation could not be
achieved by column chromatography and preparative gel
permeation chromatography. On the other hand, the reac-
tion of 3 with elemental sulfur (3.8 equiv. as S) in the pres-
ence of triethylamine afforded 8 as yellow crystals stable
under air in 71% yield (Scheme 4) [18]. Thus, the presence
of a base remarkably affects the product distribution. The
structure of 8 was determined by elemental analysis,
NMR spectroscopy and X-ray diffraction analysis.
Reaction of trihydrostannane with selenium was also
examined. Heating at reflux of a mixture of 3 and elemental
selenium in toluene overnight gave two selenium-contain-
ing cage compounds, 7 and 9 in 18% and 38% yields,
respectively, estimated by NMR spectroscopy. Recrystalli-
zation of the mixture from methanol gave 9, the structure
of which was determined by NMR spectroscopy, elemental
analysis and X-ray diffraction analysis. Treatment of 3 with
elemental selenium in the presence of triethylamine also
gave 7 and 9 in 23% and 34% yields, respectively. Although
the product distribution is slightly different from that in the
absence of triethylamine, the presence of a base does not
have a strong effect on the product distribution.
2.2. Reactions of aryltrichlorostannane 4 with alkali
chalcogenide
The most straightforward strategy for the synthesis of
trichalcogenadistannabicyclo[1.1.1]pentanes is the reaction
of trichlorostannane with alkali chalcogenide. Reaction of
trichlorostannane 4 with disodium sulfide, however, gave
dimercapto derivative 6 in 10% yield and the trans stereo-
chemistry of 6 in the solid state was confirmed by X-ray dif-
fraction analysis (Scheme 3). Thus, the third sulfur bridge
could not arch between the two tin atoms. Although a main
fraction contained monomeric products, judging from the
retention time of gel permeation chromatography, no iden-
tifiable products were obtained from the monomeric frac-
tion. On the contrary, reaction of 4 with dilithium
selenide gave a novel cage compound, tetraselenadistanna-
bicyclo[2.1.1]hexane 7, in 22% yield (Scheme 3). The 77Se
NMR spectrum of 7 showed two signals at 174.2 and
275.7 ppm with an equal intensity, suggesting that the three
selenium bridges should have one, one, and two selenium
atoms, respectively, and the structure of 7 was finally estab-
lished by X-ray diffraction analysis.
2.3. Reactions of aryltrihydrostannane 3 with elemental
chalcogen
Reaction of trihydrometallanes of Group 14 elements
with elemental chalcogen [17] is also one of the most prom-
ising methods for the synthesis of chalcogen-containing
cage compounds. Treatment of 3 with an excess amount
of elemental sulfur in toluene at 110 ꢁC gave a complex
mixture, containing a novel cage compound, 2,4,5,6,7-pen-
2.4. NMR spectroscopy
The 119Sn chemical shifts of 6–9 (6: À31.7 [19], 7: 240.5,
8: 29.7, 9: 262.0 ppm) are in the normal range for the com-
pounds having a 1,3,2,4-dichalcogenadistannetane ring.
The resonances due to the selenium atoms attached to
the tin atom range from 174 to 276 ppm. The 119Sn
tathia-1,3-distannabicyclo[3.1.1]heptane
8 (vide infra).
After purification by gel permeation chromatography, the
Scheme 2.

M. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 2729–2735
2731
Scheme 4.
NMR spectra of newly obtained chalcogen-containing
compounds, 6–9, showed signals accompanied with J(Sn–
Sn) coupling constants, the largest of which is 779 Hz, sug-
gesting no significant bonding interaction between the two
tin atoms [20]. The 1J(Sn–Se) coupling constants of 7 and 9
range from 1060 to 1316 Hz, which are in the normal range
for the compounds having a tin–selenium bond [21].
Fig. 1. ORTEP drawing of 6 with the thermal ellipsids plots (40%
probability for non-hydrogen atoms). All hydrogens and a solvent
˚
molecule were omitted for clarity. Selected bond lengths (A) and angles
(ꢁ): Sn(1)–S(1), 2.331(2); Sn(2)–S(2), 2.373(2); Sn(1)–S(3), 2.413(2); Sn(1)–
S(4), 2.511(2); Sn(2)–S(3), 2.392(2); Sn(2)–S(4), 2.381(2) S(3)–Sn(1)–S(4),
93.99(8); S(3)–Sn(2)–S(4), 95.31(8).
2.5. Molecular structures of the newly obtained chalcogen-
containing compounds
All the molecular structures of the newly obtained chal-
cogen-containing cage compounds were confirmed by X-
ray diffraction analysis. The dithiadistannetane ring of 6
is almost planar (see Fig. 1). The average angle between
the four-membered ring and the Sn–C vectors is 144ꢁ, pre-
venting steric repulsion of the two bulky aryl groups, while
that between the four-membered ring and the out-of-plane
Sn–S vectors is much narrower to be 113ꢁ. The average
bond angle around the sulfur atoms in the four-membered
ring is 85ꢁ, which is comparable to those of 1,3,2,4-dithia-
distannetanes [22]. The non-bonded distances between the
two tin atoms are longer than those of the corresponding
˚
single bonds (2.81 A) [2].
Fig. 2. ORTEP drawing of 7 with the thermal ellipsids plots (40%
The structures of 8 and 9 are similar (see Figs. 3 and 4).
Although disorder around the trichalcogenide chains of 8
and 9 was found, appropriate refinement was achieved with
the occupancies of the disordered chalcogenide chains of
60:40 for 8 and 50:50 for 9. The 1,3,2,4-dichalcogenadist-
annetane ring of 8, 7 and 9 is each found to be folded
(see Figs. 2–4). The dihedral angle between the Sn1–S1–
Sn2 and Sn1–S2–Sn2 planes in 8 is 148ꢁ, while those
between the Sn1–Se1–Sn2 and Sn1–Se2–Sn2 and between
Sn1–Se1–Sn1# and Sn1–Se1#–Sn1# in 7 and 9 are 155ꢁ
and 149ꢁ, respectively. All the lengths of the Sn–Ch
(Ch = S or Se) bonds in the four-membered rings of 7–9
are in the range of those reported for 1,3,2,4-dichalcogena-
probability for non-hydrogen atoms). All hydrogens were omitted for
clarity. Selected bond lengths (A) and angles (ꢁ): Sn(1)–Se(1), 2.5605(4);
Sn(1)–Se(2), 2.5341(4); Sn(1)–Se(3), 2.5688(4); Sn(2)–Se(1), 2.5445(4);
Sn(2)–Se(2), 2.5529(5); Sn(2)–Se(4), 2.5581(4) Se(3)–Se(4), 2.3737(5);
Sn(1)–Sn(2), 3.1453(4); Se(1)–Sn(1)–Se(2), 93.752(13); Se(1)–Sn(2)–Se(2),
93.685(8).
˚
the others (Sn1–S3–S4–S5–Sn2–S2 and Sn1–Se2–Se3–
Se4–Sn1#–Se1#, respectively) have boat conformation.
˚
The average values of 2.062 and 2.333 A for the S–S and
Se–Se bonds in 8 and 9, respectively, are in the normal
˚
range. The length of the Se–Se bond in 7 (2.3737(5) A) is
slightly longer than those in 9. The lengths of Sn1–Ch
bonds in five- or six-membered rings [2.482(7) and
˚
distannetane rings [2.38–2.49 and 2.55–2.59 A for Ch = S
˚
˚
and Se, respectively] [22]. The six-membered rings of 8
and 9 (Sn1–S3–S4–S5–Sn2–S1 and Sn1–Se2–Se3–Se4–
Sn1#–Se1, respectively) have chair conformation, while
2.453(5) A for 8, 2.5688(4) and 2.5581(4) A for 7 and
˚
2.5433(17) and 2.6098(17) A for 9] are slightly longer
than those of Sn–Ch bonds in the four-membered rings.

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M. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 2729–2735
˚
(2.81 A) [2], suggesting no significant bonding interaction,
as was suggested by the 119Sn NMR spectroscopy.
3. Conclusion
The first polychalcogenadistannabicyclo[k.l.m]alkanes
have been successfully synthesized by the chalcogenation
of trichloro- and trihydro-stannanes. The X-ray analysis
reveals the longer non-bonded distances between the two
bridgehead tin atoms than those of the normal single bonds,
suggesting no significant bonding interaction between the
two tin atoms. Further investigation on dechalcogenation
of the newly obtained polychalcogena derivatives to synthe-
size trichalcogenadistannabicyclo[1.1.1]pentanes is cur-
rently in progress.
4. Experimental
4.1. General procedures
THF and diethyl ether were distilled over sodium/ben-
zophenone. H NMR (400 MHz), 13C NMR (101 MHz),
1
119Sn NMR (149 MHz) and 77Se NMR (76 MHz) spectra
were recorded on a Bruker DRX-400 or a Bruker DPX-
400 spectrometer in CDCl3. The nJ(Sn–13C) couplings were
observed in the 13C NMR spectra as satellite signals. Wet
column chromatography (WCC) was carried out with
Kanto silica gel 60N. Preparative thin-layer chromatogra-
phy (PTLC) was carried out with Merck silica gel 60
Fig. 3. ORTEP drawing of 8 with the thermal ellipsids plots (40%
probability for non-hydrogen atoms). All hydrogens were omitted for
˚
clarity. Selected bond lengths (A) and angles (ꢁ): Sn(1)–S(1), 2.394(2);
Sn(1)–S(2), 2.411(2); Sn(1)–S(3), 2.482(7); Sn(2)–S(1), 2.403(2); Sn(2)–S(2),
2.421(2); Sn(2)–S(5), 2.453(5); S(3)–S(4), 2.057(9); S(4)–S(5), 2.067(8);
Sn(1)–Sn(2), 3.1736(8); S(1)–Sn(1)–S(2), 92.81(8); S(1)–Sn(2)–S(2),
92.36(8).
PF254
.
Preparative gel permeation chromatography
(GPC) was carried out on an LC-918 (Japan Analytical
Ind. Co., Ltd.) with JAIGEL-1H and -2H columns with
CHCl3 as the eluant. FAB mass spectra were recorded on
a JEOL JMS-700AM. IR spectrum was recorded on a
JASCO FT/IR-660 Plus at room temperature. Data for
the X-ray crystallographic analyses were collected on Bru-
ker SMART APEX diffractometer with Mo Ka radiation
˚
(k = 0.71073 A) and the structures were solved by direct
methods. All melting points were determined on a Mitam-
ura Riken Kogyo MEL-TEMP apparatus and were uncor-
rected. Elemental analyses were carried out at the
Microanalytical Laboratry of Molecular Analysis and Life
Science Center, Saitama University.
4.2. Preparation of aryltrichlorostannane 4
After treatment of a THF (40 mL) solution of 2,6-
bis(2,4,6-triisopropylphenyl)iodobenzene (ArI) [23] (2.229
g, 3.66 mmol) with t-butyllithium (1.40 N in pentane;
5.2 mL, 7.28 mmol) at À78 ꢁC, the mixture was stirred at
below À50 ꢁC for 2 h. The resulting THF solution of ArLi
was treated with stannous chloride (741 mg, 3.91 mmol) to
give a solution of arylchlorostannylene 5. After being stir-
red at below À30 ꢁC for 1 h, to a solution of 5 was added
carbon tetrachloride (5 mL, 51.6 mmol) and the resulting
mixture was warmed to room temperature. After removal
Fig. 4. ORTEP drawing of 9 with the thermal ellipsids plots (40%
probability for non-hydrogen atoms). All hydrogens were omitted for
˚
clarity. Selected bond lengths (A) and angles (ꢁ): Sn(1)–Se(1), 2.5378(6);
Sn(1)–Se(2), 2.5433(17); Sn(1#)–Se(4), 2.6098(17); Se(2)–Se(3), 2.339(2);
Se(3)–Se(4), 2.327(2); Sn(1)–Se(1#), 3.3082(6); Se(1)–Sn(1)–Se(1#),
94.129(19).
The non-bonding distances between the two bridgehead tin
˚
atoms of 8, 7 and 9 of 3.1736(8), 3.1453(4) and 3.3082(6) A,
respectively, are longer than the normal tin–tin single bond

M. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 2729–2735
2733
of materials insoluble in dichloromethane, the residue was
4.5. Reaction of aryltrichlorostannane 4 with dilithium
selenide
subjected to column chromatography (hexane followed by
ethyl acetate) to afford trichloro[2,6-bis(2,4,6-triisopropyl-
phenyl)phenyl]stannane (4) (984 mg, 45%). Compound 4:
To a THF (3 mL) solution of dilithium selenide pre-
pared from elemental selenium (25 mg, 0.32 mmol) and
Super hydrideꢂ (1 M LiEt3BH in THF; 0.65 mL,
0.65 mmol) was added a THF (3 mL) solution of aryltri-
chlorostannane 4 (148 mg, 0.21 mmol) and the resulting
mixture was stirred for 17 h at room temperature. After
removal of volatile substances, insoluble materials in chlo-
roform were filtered off. The residue was subjected to GPC
followed by PTLC (hexane:ethyl acetate = 30:1) to give
1,3-bis[2,6-bis(2,4,6-triisopropylphenyl)phenyl]-2,3,4,5-
tetraselena-1,3-distannabicyclo[2.1.1]hexane (7) (35 mg,
22%). Compound 7: mp 243–244 ꢁC (dichloromethane +
chloroform). 1H NMR: d 0.98 (d, J = 7 Hz, 24H), 1.21
(d, J = 7 Hz, 24H), 1.25 (d, J = 7 Hz, 24H), 2.55 (sept,
J = 7 Hz, 8H), 2.85 (sept, J = 7 Hz, 4H), 6.93 (s, 8H),
7.17 (d, J = 8 Hz, 4H), 7.39 (t, J = 8 Hz, 2H); 13C NMR:
d 23.46 (q), 23.95 (q), 25.87 (q), 30.77 (d, J(Sn–C) =
34 Hz), 34.28 (d), 121.38 (d), 128.90 (d), 130.30 (d, J(Sn–
C) = 62 Hz), 135.83 (s, J(Sn–C) = 28 Hz), 140.73 (s,
J(Sn–C) = 26 Hz), 146.75 (s), 147.23 (s, J(Sn–C) = 59
Hz), 149.05(s); 119Sn NMR: d À240.5 (J(Sn–Sn) = 779 Hz,
J(Sn–Se) = 1040, 1316 Hz); 77Se NMR: d 174.2, 275.7.
FAB MS, [M]+: 1516. Found: 1516.
1
mp 211–215 ꢁC (dichloromethane + methanol). H NMR:
d 1.07 (d, J = 7 Hz, 12H), 1.28 (d, J = 7 Hz, 24H), 2.60
(sept, J = 7 Hz, 4H), 2.93 (sept, J = 7 Hz, 2H), 7.07 (s,
4H), 7.31–7.48 (m, 2H), 7.62 (t, J = 7 Hz, 1H); 13C NMR:
d 22.83 (q), 23.89 (q), 25.85 (q), 30.86 (d), 34.51 (d),
121.67 (d), 130.88 (d), 131.19 (d, J(Sn–C) = 117, 121 Hz),
134.12 (s, J(Sn–C) = 40 Hz), 140.72(s), 147.12 (s, J(Sn–
C) = 78 Hz), 147.28(s), 150.52(s); 119Sn NMR: d À116.8.
Anal. Calc. for C36H49Cl3Sn: C, 61.17; H, 6.99. Found: C,
61.50; H, 7.10%.
4.3. Preparation of aryltrihydrostannane 3
To a mixture of aryltrichlorostannane 4 (125 mg, 0.18
mmol) and LiAlH4 (24 mg, 0.62 mmol) was added ether
(8 mL) and the resulting mixture was stirred for 3 h at
0 ꢁC. After removal of insoluble materials, the residue was
subjected to column chromatography (hexane:ethyl ace-
tate = 4:1) to afford trihydro[2,6-bis(2,4,6-triisopropylphe-
nyl)phenyl]stannane (3) (92 mg, 83%). Compound 3: mp
199 ꢁC (dec.)(dichloromethane + methanol). 1H NMR: d
1.07 (d, J = 7 Hz, 12H), 1.10 (d, J = 7 Hz, 12H), 1.29 (d,
J = 7 Hz, 12H), 2.62 (sept, J = 7 Hz, 4H), 2.93 (sept,
J = 7 Hz, 2H), 3.86 (s, J(Sn–H) = 1848, 1934 Hz, 3H),
7.01 (s, 4H), 7.18–7.25 (m, 2H), 7.39 (t, J = 8 Hz, 1H);
13C NMR: d 22.93 (q), 24.21 (q), 25.42 (q), 30.48 (d),
34.33 (d), 120.57 (d), 127.57 (d, J(Sn–C) = 42 Hz), 127.97
(d), 139.64 (s, J(Sn–C) = 25 Hz), 140.57 (s), 146.00 (s),
148.66 (s), 148.85 (s, J(Sn–C) = 37 Hz); 119Sn NMR: d
À384.7. IR(KBr): m(Sn–H) 1875 cmÀ1. Anal. Calc. for
C36H52Sn: C, 71.65; H, 8.68. Found: C, 71.46; H, 8.71%.
4.6. Reaction of aryltrihydrostannane 3 with elemental sulfur
To a mixture of aryltrihydrostannane 3 (120 mg,
0.20 mmol) and elemental sulfur (21 mg, 0.64 mmol as S)
was added toluene (6 mL) and then the mixture was
refluxed for 4 h. After removal of volatile substances, the
residue was subjected to GPC to give a dimeric fraction
(80 mg). The 119Sn NMR spectrum of the dimeric fraction
showed signals at À31.7 (6), À30.0, À9.6, À9.2, À7.2, 29.8
(8), 49.2 and 110.0 ppm.
4.4. Reaction of aryltrichlorostannane 4 with disodium
sulfide
4.7. Reaction of aryltrihydrostannane 3 with elemental sulfur
in the presence of triethylamine
To a mixture of aryltrichlorostannane 4 (161 mg,
0.23 mmol) and disodium sulfide (29 mg, 0.37 mmol) was
added THF (10 mL) and then the mixture was refluxed
for 21 h. After removal of insoluble materials, the residue
was subjected to GPC to afford trans-2,4-bis[2,6-bis(2,4,6-
triisopropylphenyl)phenyl]-2,4-dimercapto-1, 3,2,4-dithia-
distannetane (6) (17 mg, 10%). Compound 6: mp 219 ꢁC
To a mixture of aryltrihydroystannane 3 (65 mg,
0.11 mmol) and elemental sulfur (13 mg, 0.42 mmol as S)
in the presence of triethylamine (0.08 mL, 0.58 mmol)
was added toluene (5 mL) and then the mixture was
refluxed for 16 h. After removal of volatile substances,
the residue was subjected to GPC to give 1,3-bis[2,
6-bis(2,4,6-triisopropylphenyl)phenyl]-2,4,5,6,7-pentathia-
1,3-distannabicyclo[3.1.1]heptane (8) (53 mg, 71%). Com-
pound 8: mp 250–251 ꢁC (dichloromethane + methanol).
1H NMR: d 0.94 (d, J = 7 Hz, 12H), 0.98 (d, J = 7 Hz,
12H), 1.13 (d, J = 7 Hz, 12H), 1.26 (d, J = 7 Hz, 12H),
1.34 (d, J = 7 Hz, 24H), 2.41 (sept, J = 7 Hz, 4H), 2.43
(sept, J = 7 Hz, 4H), 2.94 (sept, J = 7 Hz, 4H), 6.90 (br s,
4H), 6.96 (br s, 4H), 7.11 (d, J = 8 Hz, 4H), 7.34 (t,
J = 8 Hz, 2H); 13C NMR: d 23.00 (q), 23.32 (q), 24.04
(q), 25.77 (q), 30.68 (d), 34.20 (d), 120.97 (d), 121.10 (d),
1
(dec.)(dichloromethane + methanol). H NMR: d 0.94 (d,
J = 7 Hz, 24H), 1.19 (d, J = 7 Hz, 24H), 1.31 (d,
J = 7 Hz, 24H), 2.54 (sept, J = 7 Hz, 8H), 2.88 (sept,
J = 7 Hz, 4H), 6.92 (s, 8H), 7.15 (d, J = 7 Hz, 4H), 7.38
(t, J = 7 Hz, 2H); 13C NMR:
d 23.07 (q, J(Sn–
C) = 66 Hz), 24.18 (q), 25.79 (q), 30.64 (d, J(Sn–
C) = 48 Hz), 34.29 (d), 121.05 (d), 129.11 (d), 130.70 (d),
134.75 (s, J(Sn–C) = 35 Hz), 144.76 (s), 145.95 (s), 147.00
(s), 149.16 (s); 119Sn NMR: d À 31.7 (J(Sn–Sn) = 666 Hz).
Anal. Calc. for C72H100S4Sn2: C, 64.96; H, 7.57. Found:
C, 63.96; H, 7.40%.

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M. Saito et al. / Journal of Organometallic Chemistry 692 (2007) 2729–2735
128.93 (d), 130.45 (d, J(Sn–C) = 68 Hz), 134.89 (s, J(Sn–
C) = 31 Hz), 144.62 (s, J(Sn–C) = 12 Hz), 146.16 (s,
J(Sn–C) = 61 Hz), 146.52 (s), 146.72 (s), 148.83 (s); 119Sn
NMR: d 29.7 (J(Sn–Sn) = 32, 64 Hz). Anal. Calc. for
C72H98S5Sn2: C, 63.53; H, 7.26. Found: C, 63.66; H,
7.20%.
tions), wR2 = 0.088 (for all reflections) for 16777 reflec-
tions and 727 parameters. GOF = 1.041.
4.12. Crystallographic data for 8
˚
0.40 · 0.20 · 0.10 mm, monoclinic, a = 27.506(2) A,
˚
˚
b = 11.2077(9) A, c = 25.658(2) A, b = 114.756(2)ꢁ, V =
3
calc = 1.259 g cmÀ3
,
Z = 4,
˚
4.8. Reaction of aryltrihydrostannane 3 with elemental
selenium
7182.9(10) A , T = 123 K,
q
space group P21/c, R1 = 0.073 (I > 2r(I), 8899 reflections),
wR2 = 0.207 (for all reflections) for 14078 reflections and
796 parameters. GOF = 1.042. Disorder around the trisul-
fide chain of 8 was found. The occupancies of the disor-
dered trisulfide chains were refined to be 0.60:0.40.
To a mixture of aryltrihydroystannane 3 (80 mg, 0.13
mmol) and elemental selenium (31 mg, 0.40 mmol) was
added toluene (6 mL) and then the mixture was refluxed
for 14 h. After removal of volatile substances, the residue
was subjected to GPC to give a dimeric fraction (57 mg)
containing 7(18 mg, 18%) and 1,3-bis[2,6-bis(2,4,6-triisopropyl-
phenyl)phenyl]-2,3,4,5,6-pentaselena-1, 3-distannabicyclo-
[3.1.1]heptane (9) (39 mg, 38%), estimated by 1H NMR
spectroscopy. Compound 9: mp 243–244 ꢁC (dichloromethane
+ methanol). 1H NMR: d 0.94 (d, J = 7 Hz, 24H), 1.17–1.30
(br m, 24H), 1.33 (d, J = 7 Hz, 24H), 2.47 (sept, J = 7 Hz,
8H), 2.92 (sept, J = 7 Hz, 4H), 6.91 (s, 8H), 7.03 (d,
J = 7 Hz, 4H), 7.29 (t, J = 7 Hz, 2H); 13C NMR: d 23.47
(q), 24.06 (q), 25.87 (q), 30.75 (d), 34.23 (d), 120.96 (d),
128.47 (d), 130.48 (d, J(Sn–C) = 57 Hz), 134.78 (s), 139.99
(s) 145.71 (s), 146.80 (s), 148.68 (s); 119Sn NMR: d À262.0
(J(Sn–Sn) = 394 Hz, J(Sn–Se) = 1002, 1288 Hz); 77Se
NMR: d 255.2, 630.3. Anal. Calc. for C72H98Se5Sn2: C,
54.19; H, 6.19. Found: C, 54.09; H, 6.22%.
4.13. Crystallographic data for 9
˚
0.50 · 0.20 · 0.05 mm, monoclinic, a = 24.1691(17) A,
˚
˚
b = 10.9409(6) A, c = 26.3617(16) A, b = 95.926(2)ꢁ, V =
3
˚
6933.6(7) A , T = 103 K,
q
calc = 1.529 g cmÀ3
,
Z = 4,
space group C2/c, R1 = 0.042 (I > 2r(I), 5218 reflections),
wR2 = 0.112 (for all reflections) for 6271 reflections and
382 parameters. GOF = 1.095. Disorder around the trisel-
enide chain of 9 was found. The occupancies of the disor-
dered triselenide chains were refined to be 0.50:0.50.
Acknowledgments
This work was partially supported by Grant-in-Aid for
Young Scientists (B) No. 17750032 (M. S.) from the Min-
istry of Education, Culture, Sports, Science, and Technol-
ogy of Japan. M.S. acknowledges a research grant from
the Asahi Glass Foundation.
4.9. Reaction of aryltrihydrostannane 3 with elemental
selenium in the presence of triethylamine
To
a
mixture of aryltrihydrostannane
3
(93 mg,
Appendix A. Supplementary material
0.15 mmol) and elemental selenium (49 mg, 0.62 mmol) in
the presence of triethylamine (0.1 mL, 0.72 mmol) was
added toluene (7 mL) and then the mixture was refluxed
for 18 h. After removal of volatile substances, the residue
was subjected to GPC to give a dimeric fraction (67 mg)
containing 7 (26 mg, 23%) and 9 (41 mg, 34%), estimated
CCDC 627566, 625924, 607160 and 625925 contain the
supplementary crystallographic data for 6, 7, 8 and 9.
These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-
mail: deposit@ccdc.cam.ac.uk. Supplementary data associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2007.02.004.
1
by H NMR spectroscopy.
4.10. Crystallographic data for 6
˚
0.40 · 0.10 · 0.10 mm, orthorhombic, a = 44.746(3) A,
3
˚
˚
˚
b = 52.011(4) A, c = 12.2152(8) A, V = 28428(4) A , T =
123 K, qcalc = 1.271 g cmÀ3, Z = 16, space group Fdd2,
R1 = 0.074 (I > 2r(I), 10614 reflections), wR2 = 0.167 (for
all reflections) for 14579 reflections and 745 parameters.
GOF = 1.036.
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