Single-ion enthalpies of transfer for Conjugate-base anions of imides in acetonitrile–methanol mixtures. Empirical correlation with semi-empirical molecular orbital calculations

Abstract

Single-ion enthalpies of transfer for conjugate-base anions of imides have been determined in acetonitrile–methanol mixtures and partitioned into constituent terms, the ‘physical’ interaction enthalpy, Δ_{tr, ph, AN → MeOH}H and the specific interaction enthalpy, Δ_{tr, SI, AN → MeOH}H. The latter enthalpies have been found to be linearly correlated with atomic charges on the carbonyl oxygen which have been determined through semi-empirical molecular orbital calculations, MNDO/PM3, and this has the physical consequence that imidide ions form hydrogen bonds with methanol at the carbonyl oxygen of the imidide ion.