Quantum chemical study of the nature of the interaction between the proton and phosphoryl compounds in the H+ ...OPX3 complex

Based on CNDO/2 (spd basis) quantum chemical calculations of the proton affinity, we propose a model describing the nature of the interaction between the proton and the molecule of phosphoryl compounds in the monocation X₃POH⁺. We have established that in the series of phosphoryl compounds, the change in the proton affinity is subject to two effects: the shift in electron density from the base to the proton, and the ionic interaction between the proton complexing agent and the phosphorus atom and substituents; and in the latter case we observe electrostatic repulsion for the substituents R, OR, NR₂ and attraction for F.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2579–2583, November, 1992.