Theoretical study on the HS activation by PtCH in the gas phase.

The reaction mechanism of the gas-phase PtCH with HS has been systematically investigated on the doublet and quartet potential energy surfaces at BPW91/6-311++ G(2 d, p)∪ SDD level. The Pt in PtCH prefers to attack S-H bond in HS. For PtCH + HS reaction, the potential energy surfaces (PESs), including three reaction pathways of hydrogen (including one and two hydrogen elimination) and methane elimination, have been explored and characterized. By contrast with hydrogen elimination, methane elimination reaction channel is energetically favorable, which is in good agreement with the experimental observation. The optimal S-H bond activation is the first step, followed by cleavage of Pt-C and Pt-S bond. About the path a and b, the lowering of activation barrier is mainly caused by the more stabilizing transition state interaction $$\varDelta E_{\text{int}}^{ \ne }$$ , which is the actual interaction energy between the deformed reactants in the transition state. [ABSTRACT FROM AUTHOR]