Quantum-chemical study of the mechanism of the influence of cations of d metals on the rate of the oxidation of phosphine by Cu(II) halides

A hypothesis concerning the formation of associates between intermediate complexes and cations has been introduced in order to account for the experimental dependence of the rate constant of the oxidation of phosphine by Cu(II) halides on the nature of the cation in the salt MCl₂ (M = Mn, Co, Ni). The quantum-chemical characteristics of the systems formed have been calculated by the Mulliken—Wolfsberg—Helmholz-SCCC method. It has been shown that the correct correlation between the electronic properties of the intermediates and the rate constant of the reaction upon the variation of M can be obtained only for a specific mechanism for the addition of M²⁺ to the complex.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 6, pp. 718–722, November–December, 1985.