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Theoretical Gas‐Phase Stabilities of α‐Trimethylsilyl‐Substituted Tertiary Carbenium Ions
Author(s) -
Grunenberg Jörg,
Laschat Sabine,
Dickner Tim
Publication year - 2003
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200300273
Subject(s) - chemistry , trimethylsilyl , hyperconjugation , hydride , gas phase , ion , group (periodic table) , carbocation , methyl group , medicinal chemistry , carbenium ion , computational chemistry , organic chemistry , inorganic chemistry , hydrogen , molecule
Theoretical hydride ion affinities in the gas phase are presented for α‐SiMe 3 ‐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)