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Activation of propane C–H and C–C bonds by a diplatinum cluster: potential energy surfaces and reaction mechanisms

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Abstract

The activation mechanism of C3H8 catalyzed by the homonuclear bimetallic Pt2 cluster has been detailedly explored on the singlet and triplet potential energy surfaces at BPW91/aug-cc-pvtz, Lanl2tz level. The C–H bond cleavage channel (dehydrogenation and the release of propylene) is kinetically predominant, whereas the C–C bond cleavage channel (demethanation and the release of ethane) should be ruled out. Furthermore, the release of propylene channel is kinetically favorable, while the dehydrogenation channel is thermodynamically preferable. Besides, both the C–H cleavage intermediate (Pt2H2C3H6b) and the C–C cleavage intermediates (CH3HPt2CHCH3 and CH3PtPtHC2H4) are thermodynamically preferred. The C–H cleavage intermediate (Pt2H2C3H6b) is kinetically favored, while the C–C cleavage intermediates (CH3HPt2CHCH3 and CH3PtPtHC2H4) are kinetically hindered. The homonuclear bimetallic Pt2 cluster toward propane exhibits higher reactivity than the Pt atom, which is in good agreement with the experimental observation.

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Acknowledgments

The authors are grateful for financial support by the National Natural Science Foundation of China (Nos. 21343001, 20976109, and 91016002), the Special Research Foundation of Doctoral Education of China (No. 20090181110046), and the Applied Foundation Research of Sichuan Province (No. 2011JY0024).

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Authors and Affiliations

  1. College of Chemical Engineering, Sichuan University, Chengdu, Sichuan, 610065, People’s Republic of China

    Ting-Yong Ju, Hua-Qing Yang, Fang-Ming Li & Xiang-Yuan Li

  2. Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, People’s Republic of China

    Chang-Wei Hu

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  1. Ting-Yong Ju
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  2. Hua-Qing Yang
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Correspondence to Hua-Qing Yang.

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Ju, TY., Yang, HQ., Li, FM. et al. Activation of propane C–H and C–C bonds by a diplatinum cluster: potential energy surfaces and reaction mechanisms. Struct Chem 25, 471–481 (2014). https://doi.org/10.1007/s11224-013-0311-4

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  • DOI: https://doi.org/10.1007/s11224-013-0311-4

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