Homolytic bond dissociation energies associated with acyl radicals and electron demands of acyl groups†
Abstract
Composite ab initio G3 and CBS-4M methods were used to calculate the homolytic bond dissociation energies (BDE) associated with various O). The structures and the vibration properties of the related acyl compounds and radicals were also obtained and discussed. It was found that the BDEs and the structures of the
O > CO–H > CO–OH > CO–SCH3 > CO–CH3 > CO–NH2. This order is not consistent with the electronegativity of each group. Therefore, it is the electron demand, not the electronegativity, that determines the substituent effects on the BDEs associated with the