Unusually Stable Vinyl Cations

Abstract

Recent results on the chemistry of persistent vinyl cations are summarized. β, β-Disilyl-substituted vinyl cations were synthesized by intramolecular addition of transient silylium ions to alkynes. The vinyl cations are stable at ambient temperature and were isolated in the form of their tetrakispentafluorophenylborate and hexabromocarboranate salts. The vinyl cations were characterized by IR and NMR spectroscopy and by X-ray crystallography. The experimental results for the α-alkyl- and α-aryl-substituted vinyl cations confirm their Y-shape structures, consisting of a linear dicoordinated, formally positively charged α-carbon atom and a trigonal planar coordinated /?-carbon atom. In addition, the spectroscopic data clearly indicate the consequences of, /?-silyl hyperconjugation in these vinyl cations. Scope and limitations of the synthetic approach to vinyl cations via addition of silylium ions to C≡C triple bonds are discussed.