Theoretical study of reactions between MH (M=B, Al) and the H<INF>2</INF>S molecule

Reaction mechanisms between MH (M=B, Al) and the H<INF>2</INF>S molecule have been theoretically studied. The G3 ab initio and DFT calculations demonstrate that only one stable addition complex (HM:SH<INF>2</INF>, M=B, Al) can be formed, and that, starting from the addition complex (HM:SH<INF>2</INF>) two parallel reaction channels have been found: one is an addition reaction to give H<INF>2</INF>MSH via the three-membered ring transition state (TS), and the other is a dehydrogenation reaction to give MSH+H<INF>2</INF> via the four-membered ring TS. Thermodynamics and Eyring transition state theory (TST) with the Wigner correction are also used to compute the thermodynamic functions, the equilibrium constants, A factors, and the rate constants of these reaction channels at 300–1500 K. The calculated results predict that the product H<INF>2</INF>BSH in the system of BH+H<INF>2</INF>S and the product AlSH+H<INF>2</INF> in the system of AlH+H<INF>2</INF>S will be mainly observed. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001