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

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Abstract

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 \(\varDelta E_{\text{int}}^{ \ne }\), which is the actual interaction energy between the deformed reactants in the transition state.

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Acknowledgments

This work was funded by the Scientific Study Project for Institutes of Higher Learning, Ministry of Education, Gansu Province (No. 2015A-140). The sixth group of college students’ science and technology innovation project (No. 113).

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  1. College of Chemistry and Chemical Engineering, Hexi University, Zhangye, China

    Qingyun Wang, Yongchun Tong, Xinjian Xu & Yongcheng Wang

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  1. Qingyun Wang
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  2. Yongchun Tong
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Correspondence to Yongchun Tong.

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Wang, Q., Tong, Y., Xu, X. et al. Theoretical study on the H2S activation by PtCH2 + in the gas phase. Struct Chem 27, 1363–1371 (2016). https://doi.org/10.1007/s11224-016-0756-3

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