Quantum chemical study of the mechanism of the reaction of tetraphosphorus with alcohol in the coordination sphere of copper(II)

We have used the CNDO Method to study ^–1-tetraphosphorus complexes of copper (II) containing MeOH, MeO^–, H₂O, HO^–, Cl^–, Br^–, I^–, formed during the new reaction of oxidative alkoxylation of P₄ to trialkylphosphates in alcohol-benzene solutions of Cu(II). We studied the nature of the activation of the coordinated molecules and ions by comparing the charges on al the atoms and the values of the total, vocalent, and ionic energies of the intramolecular and intermolecular bonds. We observed the effect of conversion of the tetraphosphorus (which does not display acid-base properties) to a strong electron acceptor, tending toward electrophilic addition of coordinated nucleophiles. The calculated quantum chemical characteristics of the tetraphosphorus complexes correlate well with experiment.D. V. Sokol'skii Institute of Organic Catalysis and Electrochemistry, Kazakh Academy of Sciences, Alma-Ata. Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 27, No. 6, pp. 659–672, November–December, 1991. Original article submitted April 19, 1990.