Theoretical study on the H2S activation by PtCH2+ in the gas phase

The reaction mechanism of the gas-phase PtCH2+ with H2S has been systematically investigated on the doublet and quartet potential energy surfaces at BPW91/6-311++G(2d, p)∪ SDD level. The Pt in PtCH2+ prefers to attack S–H bond in H2S. For PtCH2+ + H2S 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 ΔEint≠\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\varDelta E_{\text{int}}^{ \ne }$$\end{document}, which is the actual interaction energy between the deformed reactants in the transition state.