Ab initio RHF and CI calculations have been carried out on the systems LCu++CH4 and LCu2++CH4, where L = PH3, NH3 or (CH3)2O, in order to study the energetics and the mechanism of the heterolytic and homolytic cleavage of C-H bonds by mono- and bivalent coordinatively unsaturated transition metal complexes of the IB group. Various energy gradient optimizations have been performed on the reactants and several possible products, followed by MRCI calculations on the stationary structures. The results indicate that when the proton stabilization by a suitable base is accounted for heterolytic cleavage of methane by the Cu(II) system can be exothermic. Moreover, the Cu(II) system may lead to the oxidative cleavage of methane to a proton and a methyl radical, a reaction of great applicative interest.
A Theoretical-study of C-h Activation By Lcu+ and Lcu2+ Complexes
RE, Nazzareno;
1993-01-01
Abstract
Ab initio RHF and CI calculations have been carried out on the systems LCu++CH4 and LCu2++CH4, where L = PH3, NH3 or (CH3)2O, in order to study the energetics and the mechanism of the heterolytic and homolytic cleavage of C-H bonds by mono- and bivalent coordinatively unsaturated transition metal complexes of the IB group. Various energy gradient optimizations have been performed on the reactants and several possible products, followed by MRCI calculations on the stationary structures. The results indicate that when the proton stabilization by a suitable base is accounted for heterolytic cleavage of methane by the Cu(II) system can be exothermic. Moreover, the Cu(II) system may lead to the oxidative cleavage of methane to a proton and a methyl radical, a reaction of great applicative interest.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
