Abstract
Calculations at several levels of ab initio molecular orbital theory have been carried out on 20 polycyclic aryl nitrenium ions of general structure ArNH+ and containing from two to four condensed rings. Electronic interactions between the aryl ring and the NH+ group stabilize all ions relative to PhNH+ by amounts varying from 14 to 40 kcal mol−1 depending on the ring system and on the site of substitution. Apart from a few symmetrical cases, the ions exist in distinct syn and anti configurations, separated by substantial inversion barriers. At the HF/6-31G(d) level, the latter are predicted to lie in the rather narrow range of 27.8±2.0 kcal mol−1. Simple PMO analyses are presented based on the analogy with odd alternant hydrocarbon cations. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 231–243, 1999
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