Abstract: The reaction mechanism of the gas-phase Pt atom with C3H8 has been systematically investigated on the singlet and triplet potential energy surfaces at CCSD(T)//BPW91/6-311++G(d, p), Lanl2dz level. Pt atom prefers the attack of primary over secondary C-H bonds in propane. For the Pt + C3H8 reaction, the major and minor reaction channels lead to PtC3H6 + H2 and PtCH2 + C2H6, respectively, whereas the possibility to form products PtC2H4 + CH4 is so small that it can be neglected. The minimal energy reaction pathway for the formation of PtC3H6 + H2, involving one spin inversion, prefers to start at the triplet state and afterward proceed along the singlet state. The optimal C-C bond cleavages are assigned to C-H bond activation as the first step, followed by cleavage of a C-C bond. The C-H insertion intermediates are kinetically favored over the C-C insertion intermediates. From C-C to C-H oxidative insertion, the lowering of activation barrier is mainly caused by the more stabilizing transition state interaction ΔE≠int, which is the actual interaction energy between the deformed reactants in the transition state.
Keywords: Pt atom; propane; C-H bond; C-C bond; CCSD(T); BPW91
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Li, F.-M.; Yang, H.-Q.; Ju, T.-Y.; Li, X.-Y.; Hu, C.-W. Activation of Propane C-H and C-C Bonds by Gas-Phase Pt Atom: A Theoretical Study. Int. J. Mol. Sci. 2012, 13, 9278-9297.
Li F-M, Yang H-Q, Ju T-Y, Li X-Y, Hu C-W. Activation of Propane C-H and C-C Bonds by Gas-Phase Pt Atom: A Theoretical Study. International Journal of Molecular Sciences. 2012; 13(7):9278-9297.
Li, Fang-Ming; Yang, Hua-Qing; Ju, Ting-Yong; Li, Xiang-Yuan; Hu, Chang-Wei. 2012. "Activation of Propane C-H and C-C Bonds by Gas-Phase Pt Atom: A Theoretical Study." Int. J. Mol. Sci. 13, no. 7: 9278-9297.