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Ab initio MO study of benzylic cations—1. Some theoretical parameters related to the resonance demand in the Yukawa-Tsuno equation

✍ Scribed by Kazuhide Nakata; Mizue Fujio; Yoshihiro Saeki; Masaaki Mishima; Yuho Tsuno; Kichisuke Nishimoto

Publisher
John Wiley and Sons
Year
1996
Tongue
English
Weight
834 KB
Volume
9
Category
Article
ISSN
0894-3230

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✦ Synopsis

Structures of 14 kinds of benzylic cations into which are introduced various substituents at benzylic position were optimized by means of the ab initio molecular orbital method at the RHF/6-31G* level. The theoretical indices obtained associated with the resonance interaction, such as population, bond order and bond length, were compared with the resonance demand parameter ( r value) of corresponding solvolysis systems that were given by the Yukawa-Tsuno substituent effect analysis. The r value was linearly correlated with the theoretical resonance indices. and p-substituted a, a-dimethylbenzyl chlorides [R, , R2 = CH3, L = CI in equation ( 2)]. Important deviations appearing in benzylic solvolyses were reasonably referred to the increased resonance interactions in carbenium ions (intermediates)

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Ab initio MO study of benzylic cations—2
Ab initio MO study of benzylic cations—2. Steric effects on the resonance interaction and on the resonance demand in the Yukawa-Tsuno equation
✍ Kazuhide Nakata; Mizue Fujio; Yoshihiro Saeki; Masaaki Mishima; Yuho Tsuno; Kich 📂 Article 📅 1996 🏛 John Wiley and Sons 🌐 English ⚖ 640 KB

Geometries of secondary and tertiary benzylic cations, which have bulky substituents at a positions, were optimized by ab initw MO calculations at the RHF/6-31G\* and, in part, MP2/6-31G\* levels. Calculated #cu,r, which is the dihedral angle of the a-C -C bond with respect to the aromatic plane, is