Theoretical study on the temperature influences on the insertion reactions of singlet phosphinidenes XP(X=H, Li, F, Cl, OH, SH) with polar hydrogen chloride

Abstract

The insertion reaction mechanism of singlet phosphinidenes XP (X=H, Li, F, Cl, OH, SH) with polar hydrogen chloride molecule has been investigated at B3LYP/6-311+G(d, p) level in order to better understand their reactivity. Furthermore, the general statistical thermodynamics and Eyring transition state theory with Wigner correction were used to examine the temperature influences on the thermodynamic and kinetic properties of these reaction channels during the temperature range of 200–1000 K. It is concluded that with the rise of the temperature, the reaction equilibrium constant K decreases sharply, while the reaction rate constant k increases slowly for all these insertion reactions, and the reaction channel of LiP with HCl has both thermodynamic and kinetic advantages comparing with other concerned reactions, especially at high temperature.