Activation of C-H and C-C bonds of ethane by gas-phase Pt atom: Potential energy surface and reaction mechanism

作者：Li, Fang-Ming; Yang, Hua-Qing^*; Ju, Ting-Yong; Li, Xiang-Yuan; Hu, Chang-Wei

来源：Computational and Theoretical Chemistry, 2012, 994: 112-120.

DOI：10.1016/j.comptc.2012.06.021

• Pt atom
• Ethane
• C-H bond
• C-C bond
• BPW91
• CCSD(T)

The reaction mechanism of the gas-phase Pt atom with C2H6 has been systematically studied on the singlet and triplet potential energy surfaces at CCSD(T)//BPW91/6-311++G(d, p), Lan12dz level. For the formation of the main products, PtC2H4 + H-2 and (H)(2)Pt + C2H4, the minimal energy reaction pathway involves the rate-determining step of the release of a H2 or ethene molecule by a reductive elimination mechanism at the exit. For the formation of the side products, PtCH2 + CH4, the optimal pathway proceeds through the a-complex cis-HPtC2H5 from initial C-H bond cleavage, which assists the C-C sigma-bond metathesis. This reactivity mode is complementary for the classical reactivity picture through the C-C cleavage intermediate M(CH3)(2). Besides, these results are in qualitative agreement with the experimental results, in which the C-H insertion product is experimentally observed and the C-C insertion product is not formed in observable quantity.

• 出版日期2012-8-15
• 单位四川大学