Abstract
AbstractTheoretical hydride ion affinities in the gas phase are presented for α‐SiMe3‐substituted tertiary carbenium ions. Thermodynamic stabilization of the ”nascent“ ions by a single trimethylsilyl group is weaker than by a tert‐butyl group but comparable to the effect of a methyl group. In the case of the cyclopropenylium cation, the stabilization by a trimethylsilyl group even exceeds the effectiveness of a tert‐butyl group. Compliance constants are used to quantify the chemical concept of hyperconjugation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
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