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Angew. , I n f . Ed. Engl. 1992,31, 1354. ; Matsumoto, N. Appl. Phys. Lett. 1992, 60, 2744. ; Finger, C. M. ; Polborn, K. Angew. , I n t . Ed. Eng. 1993, 32, 1054. ( I / ) Clabo, D. ; Schaefer 111, H. F. J . Am. Chem. 1986,108, 4344. ; Kalcher, J. J . Chem. , Chem. Commun. 1987, 809; Sax, A. ; Kalcher, J. J. Comput. Chem. 1989,10, 309. ; Nakano, M. Angew. , l n t . Ed. Engl. 1988,27, 1081. ; Nagashima, M. J . Chem. , Chem. Commun. 1992, 1302. (146) Nagase, S. Pure Appl. Chem. 1993, 65, 675. ; Aoki, M.

6 2. I 34 AKIRA SEKlGUCHl AND HlDEKl SAKURAI R A A (25) (29) I$: R (26) RO R hvhv (A (A = 360-380 > 460 nm) nm)* )$fR R R+ R (30) R SCHEME 20 double bonds. The large negative activation entropy suggests the significant decrease of the freedom in the transition state to form 25. All attempts to trap the hexasila-Dewar benzene 29 with methanol or sulfur failed, probably due to the rapid intramolecular reaction to regenerate 25. Irradiation of hexagermaprismane26 (R = 2,6-i-Pr&H3) also produced new absorption bands at 342,446, and 560 nm due to hexagerma-Dewar benzene 30 at low temperature.

BuMezSiSi)8(15), silyl substituents decrease the strain in the polyhedrane (14). Thus, the synthesis of tetrasilatetrahedrane has been accomplished by use of the "supersilyl" group (tert-Bu3Si)(10). The dehalogenation of tert-Bu3Si-SiC13 with sodium at 80°C led to the formation of various products: 1,2-bis(supersilyl)disilane (31) and tris(supersi1yl)cyclotrisilane (32). N + benzene 80 'C (31) I tricycle[ I . 02,4]tetrasilane(34) as yellow-orange crystals in 57% yield (Scheme 21). The reaction mechanism for 34 is not clear.

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