Preparation of the First Tricoordinate Silyl Cation
Preparation of the First Tricoordinate Silyl Cation
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第一个三配位甲硅烷基阳离子的制备
DOI：
10.1002/chin.200144264
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发表时间：
2001
期刊：
影响因子：
--
通讯作者：
S. Zhang
中科院分区：
文献类型：
--
作者：
J. B. Lambert;Yan Zhao;S. Zhang
经过 20 年的一系列发现，第一个三配位甲硅烷基阳离子的制备成为可能。该材料的极高亲电性需要保护其免受各种亲核试剂的影响。只有芳烃的亲核性足够低才能用作溶剂。四(五氟苯基)硼酸盐提供了最少的亲核阴离子。所有操作都必须在惰性气氛中进行，主要是为了防潮。需要空间大的取代基（例如异丙叉基）来保护阳离子，甚至免受优化的溶剂和阴离子的影响。通过亲电子试剂与烯丙基双键的反应以及烯丙基加合物的挤出，由烯丙基三三甲苯基硅烷产生三三甲苯基甲硅烷基鎓离子。版权所有 © 2001 约翰·威利父子有限公司
The preparation of the first tricoordinate silyl cation was made possible by a sequence of discoveries over a 20 year period. The extremely high electrophilicity of the material required protection from all manner of nucleophiles. Only arenes had sufficiently low nucleophilicity to serve as solvent. Tetrakis(pentafluorophenyl) borate provided the least nucleophilic anion. All manipulations had to be carried out in an inert atmosphere, primarily as protection from moisture. Sterically bulky substituents such as mesityl were needed to protect the cation even from the optimized solvent and anion. The trimesitylsilylium ion was produced from allyltrimesitylsilane by reaction of electrophiles with the allyl double bond and extrusion of the allyl adduct. Copyright © 2001 John Wiley & Sons, Ltd.