PHOTOINDUCED ELECTRON-TRANSFER OXYGENATION OF 1,2-DISILETENE

被引:11
作者
AKASAKA, T [1 ]
SATO, K [1 ]
KAKO, M [1 ]
ANDO, W [1 ]
机构
[1] UNIV TSUKUBA,DEPT CHEM,TSUKUBA,IBARAKI 305,JAPAN
关键词
D O I
10.1016/0040-4020(92)85004-X
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Photo-induced electron transfer oxygenation of 3-phenyl-1,1,2,2-tetramesityl-1,2-disilet-3-ene (1) in acetonitrile-methylene chloride afforded the corresponding 1,2-dioxa-3,6-disilin (2) in moderate yield as a dioxygen insertion product into a silicon-silicon sigma-bond together with 1-oxa-2,5-disilolene (3). The results are reasonably accounted for by an electron transfer from disiletene 1 to the excited singlet state of the sensitizer to form a radical ion pair followed by addition of oxygen. Interestingly, a remarkable solvent effect was observed in the product ratio of dioxadisilin 2 and oxadisilolene 3 as a monooxygenated product. The solvent acetonitrile, acting as a nucleophile, participates for predominant formation of 2. Meanwhile, in the absence of acetonitrile, 3 was afforded as a major product. The conceivable mechanism is proposed.
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页码:3283 / 3292
页数:10
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