Godwin Sik Cheung Choy

Potential Energy Surface and Electron Density Analysis of Phosphorus Analogues of Aromatic and Aliphatic Diazonium Ions

Abstract Potential energy surface analyses at ab initio levels including electron correlation are reported for the phosphorus analogues of diazonium ions, RXY+ with X, Y [dbnd] N, P. Protonated, methylated, and phenylated systems are compared with focus on the question regarding end-on versus edge-on coordination. Diphosphonium and phosphoazonium ions are predicted to be more stable toward dissociation than the diazonium ions. The calculated spectroscopic data may assist in their detection. Electronic density distributions of RXY+ were analyzed in a variety of ways and with a new energy decomposition method. Charge distributions are contrasted with Lewis notations. CN and CP-bonded ions show clearly distinct bonding patterns.