PENTACOORDINATED SILICON ANIONS - SYNTHESIS AND REACTIVITY .1.

被引:47
作者
BREFORT, JL [1 ]
CORRIU, RJP [1 ]
GUERIN, C [1 ]
HENNER, BJL [1 ]
WONGCHIMAN, WWC [1 ]
机构
[1] UNIV MONTPELLIER 2,CNRS,UA 1097,HETEROCHIM & AMINO ACIDES LAB,PL EUGENE BATAILLON,F-34095 MONTPELLIER 05,FRANCE
关键词
D O I
10.1021/om00157a016
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Pentacoordinated anionic siliconates Ph3Si(OMe)2-K+(18-crown-6), Ph2Si(OMe)3-K+(18-crown-6), Ph3SiF2-K+(18-crown-6), and MePhSiF3- K+(18-crown-6) reacted with nucleophiles (RMgX, RLi, ROLi, LiAlH4) to give the neutral tetravalent substituted silicon derivatives. Reactivity comparisons between Ph3SiX2-K+(18-crown-6) and Ph3SiX (X = F, OMe) showed that the pentavalent anionic species is more reactive than the tetravalent analogue toward nucleophiles. Hydrolysis reactions of Ph3SiF2-K+(18-crown-6) and Ph3Si(OMe)2-K+(18-crown-6) gave respectively Ph3SiF and a mixture of Ph3SiOMe and Ph3SiOH. Results clearly indicate that nucleophilic attack at pentacoordinated silicon species is a general process. Moreover, the data point out the enhanced reactivity of these species that may mainly arise from a general loosening of the bonds around silicon. © 1990, American Chemical Society. All rights reserved.
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页码:2080 / 2085
页数:6
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