Reaction of ClF and Cl2 with PH2X: The oxidation of P(III) to P(V)

Abstract

Abstract Ab initio MP2/aug′-cc-pVTZ calculations have been performed to examine the oxidation of P(III) to P(V) in reactions involving FCl and Cl2 as the oxidizing agents of PH2X molecules, for X\u202f=\u202fF, Cl, H, NC, and CN. Stable P(III) binary complexes and P(V) molecules, and the transition states which connect these minima exist on all (PH2X\u202f+\u202fClF) and (PH2X\u202f+\u202fCl2) potential surfaces. Profiles of binding energies, 31P chemical shieldings, and EOM-CCSD spin-spin coupling constants J(P-Cl) on these surfaces exhibit similar patterns, with minimum values for transition structures.