Oxygen donor potential of carbonyl oxide and dioxirane: a DFT study

The oxygen donor potentials of carbonyl oxide and dioxirane have been exami ned in the gas phase B3LYP/6-31G(d, p) for their reactions with ethylene, p ropene, cis-2-butene, trans-2-butene and 1-cyano-ethylene. Our results have shown that the electronic and structural characteristics of the substituen ts alter the activation barriers. The effect of the solvent has been modele d with the SCIPCM method for ethylene. The energy barriers for the reaction s of carbonyl oxide and dioxirane with ethylene have not altered in solutio n even though drastic changes in the electronic behavior of carbonyl oxide have been determined. An improved solvent model where specific interactions will be taken into account is suggested for further studies. (C) 1999 Else vier Science B.V. All rights reserved.