Comment on the Paper 'On the Limits of Highest-Occupied Molecular Orbital Driven Reactions:The Frontier Effective-for-Reaction Molecular Orbital Concept'

摘要

In a recent paper,da Silva et al.argued that Fukui's concept of frontier orbitals2 was obsolete and unsatisfactory.To corroborate this statement,they consider the acidity of carboxylic acids,phenols,and alcohols.For this purpose,the orbital energies of the highest occupied molecular orbitals (HOMOs) and some specific molecular orbitals lower than HOMOs are compared with the experimental pK_a values.It turned out (not surprisingly!) that the latter gave better correlations with the measured data.Da Silva et al.found it necessary to baptize these specific MOs as frontier effective-for-reaction MOs (FERMOs),claiming that it is a new concept.This is not true,as expounded in the present comment.