Scientific article
English

Steric Effects on Reaction Rates. VI. Application of a New MM2 Force-Field for Carbenium Ions to Solvolysis Rates of Secondary p-Toluenesulfonates

Published inHelvetica chimica acta, vol. 68, no. 1, p. 119-125
Publication date1985
Abstract

An empirical force-field for carbenium ions has been incorporated in Allinger's MM2 programme. Structural parameters of secondary carbenium ions calculated by this method are compared with those obtained with Schleyer's BIGSTRN calculations. The strain changes occurring upon solvolysis of secondary p-toluenesulfonates are evaluated by means of this force-field and correlated with the rate constants for solvolysis. The equation for correlation of acetolysis, relative to cyclohexyl p-toluenesulfonate, of 28 kc substrates is ΔG+(rel) = 0.67 ΔEst - 0.20 (r = 0.958).

Citation (ISO format)
MULLER, Paul, MAREDA, Jiri. Steric Effects on Reaction Rates. VI. Application of a New MM2 Force-Field for Carbenium Ions to Solvolysis Rates of Secondary p-Toluenesulfonates. In: Helvetica chimica acta, 1985, vol. 68, n° 1, p. 119–125. doi: 10.1002/hlca.19850680115
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Journal ISSN0018-019X
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