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Theoretical mechanistic study of the reaction of the methylidyne radical with methylacetylene

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Abstract

A detailed doublet potential energy surface for the reaction of CH with CH3CCH is investigated at the B3LYP/6-311G(d,p) and G3B3 (single-point) levels. Various possible reaction pathways are probed. It is shown that the reaction is initiated by the addition of CH to the terminal C atom of CH3CCH, forming CH3CCHCH 1 (1a,1b). Starting from 1 (1a,1b), the most feasible pathway is the ring closure of 1a to CH3–cCCHCH 2 followed by dissociation to P 3 (CH3–cCCCH+H), or a 2,3 H shift in 1a to form CH3CHCCH 3 followed by C–H bond cleavage to form P 5 (CH2CHCCH+H), or a 1,2 H-shift in 1 (1a, 1b) to form CH3CCCH2 4 followed by C–H bond fission to form P 6 (CH2CCCH2+H). Much less competitively, 1 (1a,1b) can undergo 3,4 H shift to form CH2CHCHCH 5. Subsequently, 5 can undergo either C–H bond cleavage to form P 5 (CH2CHCCH+H) or C–C bond cleavage to generate P 7 (C2H2+C2H3). Our calculated results may represent the first mechanistic study of the CH + CH3CCH reaction, and may thus lead to a deeper understanding of the title reaction.

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Acknowledgments

This work is supported by the National Natural Science Foundation of China (nos. 20773048, 21073075)

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Authors and Affiliations

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, People’s Republic of China

    Lili Zhang, Hui-ling Liu, Xu-ri Huang, Yan Li, Yan-bo Sun & Chia-chung Sun

  2. JiLin Provincial Instritute of Education, Changchun, 130022, People’s Republic of China

    Guang-Hui Yang

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  1. Lili Zhang
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  2. Hui-ling Liu
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  5. Yan Li
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Correspondence to Xu-ri Huang.

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Zhang, L., Liu, Hl., Yang, GH. et al. Theoretical mechanistic study of the reaction of the methylidyne radical with methylacetylene. J Mol Model 17, 3173–3181 (2011). https://doi.org/10.1007/s00894-011-0979-6

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  • DOI: https://doi.org/10.1007/s00894-011-0979-6

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