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The (Me5C5)Si+ Cation: A Stable Derivative of HSi+

Science  06 Aug 2004:
Vol. 305, Issue 5685, pp. 849-851
DOI: 10.1126/science.1099879

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Abstract

The reaction of decamethylsilicocene, (Me5C5)2Si, 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 π complex with an η5-pentamethylcyclopentadienyl ligand bound to a bare silicon center. The 29Si nuclear magnetic resonance at very high field (δ = – 400.2 parts per million) is typical of a π complex of divalent silicon. The (η5-Me5C5)Si+ cation in 2 can be regarded as the “resting state” of a silyliumylidene-type (η1-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-{(η1-Me5C5)[N(SiMe3)2]Si}2 (3).

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