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Originally published in Science Express on 1 July 2004
Science 6 August 2004:
Vol. 305. no. 5685, pp. 849 - 851
DOI: 10.1126/science.1099879
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Reports

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

Peter Jutzi,* Andreas Mix, Britta Rummel, Wolfgang W. Schoeller, Beate Neumann, Hans-Georg Stammler

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 {pi} complex with an {eta}5-pentamethylcyclopentadienyl ligand bound to a bare silicon center. The 29Si 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).

Faculty of Chemistry, University of Bielefeld, Universitätsstrasse 25, D-33615 Bielefeld, Germany.

* To whom correspondence should be addressed. E-mail: peter.jutzi{at}uni-bielefeld.de

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