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http://dx.doi.org/10.5012/bkcs.2005.26.8.1177

An ab initio Study on the Molecular Elimination Reactions of Methacrylonitrile  

Oh, Chang-Young (Department of Chemistry and Research Institute for Basic Sciences, Kangwon National University)
Park, Tae-Jun (Department of Chemistry, Dongguk University)
Kim, Hong-Lae (Department of Chemistry and Research Institute for Basic Sciences, Kangwon National University)
Publication Information
Bulletin of the Korean Chemical Society / v.26, no.8, 2005 , pp. 1177-1184 More about this Journal
Abstract
Ab initio quantum chemical molecular orbital calculations have been performed for the unimolecular decomposition of methacrylonitrile ($CH_3C(CN)=CH_2$), especially for HCN and $H_2$ molecular elimination channels. Structures and energies of the reactants, products, and relevant species along the individual reaction pathways were determined by MP2 gradient optimization and MP4 single point energy calculations. Direct four-center elimination of HCN and three-center elimination of H2 channels were identified. In addition, H or CN migration followed by HCN or H2 elimination channels via the methylcyanoethylidene intermediate was also identified. Unlike the case of crotonitrile previously studied, in which the dominant decomposition process was the direct three-center elimination of HCN, the most important reaction pathway should be the direct threecenter elimination of $H_2$ in the case of methacrylonitrile.
Keywords
Ab initio; Molecular elimination; Methacrylonitrile;
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