The (Me5C5)Si+ cation: A stable derivative of HSi+
The (Me5C5)Si+ cation: A stable derivative of HSi+
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DOI：
10.1126/science.1099879
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发表时间：
2004-08-06
期刊：
影响因子：
56.9
通讯作者：
Stammler, HG
中科院分区：
文献类型：
--
作者：
Jutzi, P;Mix, A;Stammler, HG
十甲基硅茂（Me-5 C-5）（2）Si与质子转移试剂Me 5 C5 H2 + B（C6 F5）（4）-反应生成盐（Me 5 C5）Si+ B（C6 F5）（4）-（2），其可以分离为无色固体，在没有空气和水分的情况下稳定。晶体结构揭示了阳离子π络合物的存在与η（5）-五甲基吡啶配体结合到裸硅中心。极高场（delta =-400.2ppm）下的Si-29核磁共振是二价硅的pi复合物的典型特征。2中的（eta（5）-Me 5C 5）Si+阳离子可以被认为是亚甲硅烷基型（eta（1）-Me 5C 5）Si+阳离子的“静止状态”。2的可用性在有机硅化学中开辟了新的合成途径。例如，2与双（三甲基甲硅烷基）氨基锂反应，得到二硅烯E-{（eta（1）-Me 5C 5）[N（SiMe 3）（2）]Si}（2）（3）。
The reaction of decamethylsilicocene, (Me-5 C-5)(2)Si, with the proton-transfer reagent Me5C5H2+ B(C6F5)(4)- produces the salt (Me5C5)Si+ B(C6F5)(4)- (2), which can be isolated as a colorless solid that is stable in the absence of air and moisture. The crystal structure reveals the presence of a cationic pi complex with an eta(5)-pentamethylcyclopentadienyl ligand bound to a bare silicon center. The Si-29 nuclear magnetic resonance at very high field (delta = -400.2 parts per million) is typical of a pi complex of divalent silicon. The (eta(5)-Me5C5)Si+ cation in 2 can be regarded as the "resting state" of a silyliumylidene-type (eta(1)-Me5C5)Si+ cation. The availability of 2 opens new synthetic avenues in organosilicon chemistry. For example, 2 reacted with lithium bis(trimethylsilyl)amide to give the disilene E-{(eta(1)-Me5C5)[N(SiMe3)(2)]Si}(2) (3).