title: Activation of propane C-H and C-C bonds by gas-phase Pt atom: a theoretical study.
abstract: The reaction mechanism of the gas-phase Pt atom with C(3)H(8) 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 + C(3)H(8) reaction, the major and minor reaction channels lead to PtC(3)H(6) + H(2) and PtCH(2) + C(2)H(6), respectively, whereas the possibility to form products PtC(2)H(4) + CH(4) is so small that it can be neglected. The minimal energy reaction pathway for the formation of PtC(3)H(6) + H(2), 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.
authors.affiliation: College of Chemical Engineering, Sichuan University, Chengdu, Sichuan, 610065, China.
authors.forename: Fang-Ming
authors.initials: FM
authors.lastname: Li
authors.affiliation: College of Chemical Engineering, Sichuan University, Chengdu, Sichuan, 610065, China.
authors.forename: Hua-Qing
authors.initials: HQ
authors.lastname: Yang
authors.affiliation: College of Chemical Engineering, Sichuan University, Chengdu, Sichuan, 610065, China.
authors.forename: Ting-Yong
authors.initials: TY
authors.lastname: Ju
authors.affiliation: College of Chemical Engineering, Sichuan University, Chengdu, Sichuan, 610065, China.
authors.forename: Xiang-Yuan
authors.initials: XY
authors.lastname: Li
authors.affiliation: Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China.
authors.forename: Chang-Wei
authors.initials: CW
authors.lastname: Hu
mesh_terms: D008956:Models, Chemical; D011407:Propane / Q000737:chemistry*
chemical_list: D011407:Propane