Reactions of singlet phosphinidene and its hydroxy derivative with polar molecule hydrogen fluoride

Abstract

The reaction mechanism of singlet phosphinidene and its hydroxy derivative with hydrogen fluoride has been investigated at the HF/6-311+G(d,p) and CCSD (T)/6-311+G(d,p) levels etc. in order to better understand their reactivity. The research results show both of them have two parallel reaction channels: channel (1) (or (3)) is an addition reaction with a three-membered ring transition state (TS) and channel (2) (or (4)) is a dehydrogenation (or dehydration) reaction with a four-membered ring TS. Furthermore, the thermodynamic and kinetic properties of these reaction channels were also examined, using the general statistical thermodynamics and Eyring transition state theory with Wigner correction. It is concluded that channel 1 is thermodynamically favoured over channel (2) especially at low temperature, and is kinetically favoured over channel (2) especially at high temperature. Moreover, it also favours these over reaction (3) while the singlet phosphinidene is substituted by the hydroxy group.