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Bond dissociation energies and the Hammett correlation, Part 1: Remotely substituted aromatic compounds and vitamin E
Author(s) -
Luo YuRan
Publication year - 2002
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.10075
Subject(s) - chemistry , hammett equation , substituent , bond dissociation energy , dissociation (chemistry) , reaction rate constant , computational chemistry , basis set , covalent bond , reactivity (psychology) , medicinal chemistry , organic chemistry , density functional theory , kinetics , medicine , physics , alternative medicine , pathology , quantum mechanics
Four hundred and seventy nine experimental values of XZ bond dissociation energies (BDEs) of para‐, ortho‐, meta‐, and multisubstituted aromatic compounds were reproduced by the following simple equations:Here X represents a wide variety of univalent atoms or groups; Y is one or several various remote substituents; and Z represents an oxygen, nitrogen, carbon, or sulfur atom. DH 0 (XZC 5 H 6 ) is a known reference/anchor point for a series of XZ bonds. E sr is the remote conjugation energy between the substituents and the reaction center (broken bond), and can be expressed as a Hammett‐type correlation. σ + (Y) is the Brown–Okamoto constant of a substituent Y or the sum of several substituent constants. The Hammett slope or reaction constant ρ is a linear function of the difference between the covalent potentials V x (Z) and V x (X). It has been found thatandThe set of equations are very powerful for the prediction of BDEs, chemical reactivity, and reaction center (or active site) in antioxidants, nutrients, pharmaceuticals, toxicants, carcinogens, and explosives. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 453–466, 2002