Thermodynamic and Kinetic Studies on the Sill ＋ XH3 （X=N, P） Reactions

Based on the quantum chemical study of the silylidyne insertion reaction with NH3 or PH3, the general statistical thermodynamics and Eyring transition state theory with Wigner correction are used to compute the changes of thermodynamic functions, equilibrium constants, A factors and rate constants of the two reactions in the temperature range 200-2000K. The results show that both of these reactions are thermodynamically dominant at low temperatures and kinetically favored at higher temperatures. The comparison between these two reactions shows that the Sill reaction with NH3 is more exothermic than Sill with PH3, while the rate constant of Sill reaction with NH3 is lower than that of Sill with PH3 at the same temperature.