Theoretical investigation on reactivity of singlet radical phosphinidene: reaction mechanism of its reacting with polar hydrogen chloride molecule

Abstract

We have obtained two initial complexes (linear HPHCl and HPClH), and studied the reaction mechanism of singlet radical phosphinidene with polar hydrogen chloride molecule by ab initio molecular orbital theory at HF/6-31G(d), MP2(fc)/6-311+G(d,p) and G2 levels. Moreover, we have also calculated the thermodynamic and kinetic functions from 100 to 1100K in steps of 200K making use of the statistical thermodynamics and Eyring transition state theory with Wigner correction. It is concluded that there are two parallel reaction paths: Reaction A, an addition reaction which has the transition state (TS) formed by three-membered ring, has thermodynamic favor but does not have kinetic favor at low temperatures. However, it has both thermodynamic favor and kinetic favor at high temperatures comparing with Reaction B, a dehydrogenation reaction which has the TS formed by four-membered ring.