title: Theoretical mechanistic study of the reaction of the methylidyne radical with methylacetylene.
abstract: A detailed doublet potential energy surface for the reaction of CH with CH(3)CCH 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 CH(3)CCH, forming CH(3)CCHCH 1 (1a,1b). Starting from 1 (1a,1b), the most feasible pathway is the ring closure of 1a to CH(3)-cCCHCH 2 followed by dissociation to P                         (                            3                         )(CH(3)-cCCCH+H), or a 2,3 H shift in 1a to form CH(3)CHCCH 3 followed by C-H bond cleavage to form P                         (                            5                         )(CH(2)CHCCH+H), or a 1,2 H-shift in 1 (1a, 1b) to form CH(3)CCCH(2)                         4 followed by C-H bond fission to form P                         (                            6                         )(CH(2)CCCH(2)+H). Much less competitively, 1 (1a,1b) can undergo 3,4 H shift to form CH(2)CHCHCH 5. Subsequently, 5 can undergo either C-H bond cleavage to form P                         (                            5                         ) (CH(2)CHCCH+H) or C-C bond cleavage to generate P                         (                            7                         ) (C(2)H(2)+C(2)H(3)). Our calculated results may represent the first mechanistic study of the CH + CH(3)CCH reaction, and may thus lead to a deeper understanding of the title reaction.
authors.affiliation: State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China. lilizhang2010fly@gmail.com
authors.forename: Lili
authors.initials: L
authors.lastname: Zhang
authors.forename: Hui-Ling
authors.initials: HL
authors.lastname: Liu
authors.forename: Guang-Hui
authors.initials: GH
authors.lastname: Yang
authors.forename: Xu-Ri
authors.initials: XR
authors.lastname: Huang
authors.forename: Yan
authors.initials: Y
authors.lastname: Li
authors.forename: Yan-Bo
authors.initials: YB
authors.lastname: Sun
authors.forename: Chia-Chung
authors.initials: CC
authors.lastname: Sun
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002625:Chemistry, Organic; D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry*; D007700:Kinetics; D008962:Models, Theoretical; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D000480:Alkynes; D005609:Free Radicals; C022030:methylacetylene