K. Mochida et al. / Journal of Organometallic Chemistry 673 (2003) 84Á
/94
93
4.9. Reaction of 1,2-digermacyclohexa-3,5-diene (2)
with TCNE
93.5, 99.9, 113.3, 114.1, 125.1, 126.1, 126.2, 126.4, 127.1,
127.5, 128.1, 129.4, 130.8, 131.4, 137.1, 138.0, 138.2,
139.0, 139.6, 143.8, 146.0, 146.4, 148.8; MS m/z 648; UV
1
A solution of 1,1,2,2-tetramethyl-1,2-digerma-3,4,5,6-
tetraphenylcyclohexa-3,5-diene (2) (0.22 g, 0.4 mmol)
and TCNE (0.4 mmol) in CH2Cl2 (6 ml) was placed in a
Pyrex tube under argon and sealed. The color of the
solution changed from yellow to green. The Pyrex tube
was heated at 90 8C for 4 h to give 4-amino-5,6-dicyano-
2,2,11,11-tetramethyl-1,8,9,10-tetraphenyl-3-aza-2,11-
digermatricyclo[6.2.1.03,7]undeca-4,6,9-triene (7, 3%),
2,2,3,3-tetracyano-7,7,dimethyl-1,4,5,6-tetraphenyl-7-
germabicyclo[2,2,1]hepta-5-ene (8, 9%), 1,1,3,3-tetra-
methyl - 4,5,6,7 - tetraphenyl - 2 - oxa - 1,3 - digermacyclo-
hepta-4,6-diene (9, 16%), 2,2,4,4,6,6-hexamethyl-1,3,5-
trioxa-2,4,6-trigermacyclohexane (10, trace), and some
unidentified products. The rest of 2 (45%) was recovered
unchanged from the CH2Cl2 solution. Concentration of
the reaction mixture by evaporation of CH2Cl2 followed
by both preparative GPC and TLC (silica gel) gave pure
7. 7: 1H-NMR (d, CDCl3) 0.33 (s, 3H), 0.71 (s, 3H), 0.72
(CH2Cl2) lmax 345 nm (log o 3.27). 12: H-NMR (d,
CDCl3) 0.19 (s, 3H), 0.27 (s, 3H), 0.65 (s, 3H), 0.78 (s,
3H), 3.98 (broad s, 2H), 6.45Á
/
7.16 (m, 20H); 13C-NMR
(d, CDCl3) ꢂ1.8, 0.9, 2.0, 2.2, 3.9, 12.7, 71.6, 106.3,
/
112.7, 113.9, 125.8, 126.3, 127.1, 127.4, 127.9, 128.1,
128.2, 129.1, 130.5, 130.7, 134.8, 137.5, 138.8, 139.2,
145.4, 146.3, 154.7; MS m/z 646; UV (CH2Cl2) lmax 269
nm (log o 4.48).
4.11. Reactions of 1,2-dimetallacyclohexa-3,5-dienes
with TCNE in the presence of trapping reagents
As a representative example, the reaction of 1,1,2,2-
tetramethyl-1,2-disila-3,4,5,6-tetraphenylcyclohexa-3,5-
diene (1) with TCNE in the presence of 2,3-dimethyl-
1,3-butadiene is described. A solution of 1,1,2,2-tetra-
methyl-1,2-disila-3,4,5,6-tetraphenylcyclohexa-3,5-diene
(1) (0.01 mmol), TCNE (0.01 mmol), and 2,3-dimethyl-
buta-1,3-diene (0.08 mmol) in CD2Cl2 (0.6 ml) was
placed in a NMR tube under argon and sealed. The
color of the solution changed from yellowish-green to
reddish-brown. The reaction products were examined by
(s, 3H), 1.10 (s, 3H), 3.86 (broad s, 2H), 6.76Á
/
7.65 (m,
20H); 13C-NMR (d, CDCl3) ꢂ
/
0.5, 0.8, 1.7, 1.9, 56.2,
76.6, 93.2, 94.6, 113.1, 114.2, 126.3, 126.3, 127.1, 127.3,
128.1, 128.2, 128.3, 130.4, 130.6, 130.8, 135.1, 137.7,
138.8, 139.2, 144.6, 145.0, 146.5, 155.0; MS m/z 692; UV
(CH2Cl2) lmax 287 nm (log o 3.49).
NMR and GCÁMS spectra analysis.
/
4.10. Reaction of 1-germa-2-silacyclohexa-3,5-diene (3)
with TCNE
Acknowledgements
The authors thank Mitsubishi Material Co., Ltd, for
providing us tetrachlorogermane.
A solution of 1,1,2,2-tetramethyl-1-germa-2-sila-
3,4,5,6-tetraphenylcyclohexa-3,5-diene (3) (0.207 g, 0.4
mmol) and TCNE (0.4 mmol) in CH2Cl2 (6 ml) was
placed in a Pyrex tube (fꢁ1 cm) under argon and
/
References
sealed. The color of the solution changed from yellow-
ish-green to reddish-brown. The Pyrex tube was heated
at 90 8C for 3 h to give 4-amino-5,6-dicyano-2,2,11,11-
tetramethyl-1,8,9,10-tetraphenyl-3-aza-11-germa-2-sila-
tricyclo[6.2.1.03,7]undeca-4,6,9-triene (11, 5%), 4-amino-
5,6-dicyano-2,2,11,11-tetramethyl-1,8,9,10-3-aza-11-
germa-2-silatricyclo[6.3.01,8.03,7]undeca-4,6,9-triene (12,
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clohepta-4,6-diene (13, 23%), and some unidentified
products. The color of the solution changed from
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dentified products were also detected. The rest of 3
(46%) was recovered unchanged from the CH2Cl2
solution. Concentration of the reaction mixture by
evaporation of CH2Cl2 followed by both preparative
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/
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/
/