کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
5417257 1506926 2009 5 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Theoretical study on the reaction mechanism of vinyl radical with formyl cyanide
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
Theoretical study on the reaction mechanism of vinyl radical with formyl cyanide
چکیده انگلیسی
A detailed computational study is performed on the radical-molecule reaction between the Vinyl radical (C2H3) and formylcyanide (HCOCN). At the B3LYP/6-311G** and CCSD levels, the barrier of H-abstraction to provide (C2H4 + COCN) is 19.2 and 35.1 kJ/mol, respectively. The barrier of the addition to form H2CCHCOHCN is 9.1 and 15.5 kJ/mol, respectively. Subsequently, there is only one highly competitive dissociation pathway for H2CCHCOHCN: the formation of C2H4 + COCN via the intermediate H2CCH2COCN. Thanks to the influence of the strong electron acceptor-CN to the acyl, both the involved transition states and intermediates of the H2CCHCOHCN evolution lie energetically lower than the entrance addition transition state, the addition-elimination is more competitive than the direct H-transfer which results in C2H3 + HCOCN reaction, which ridiculously contradict to previous expectation. The present results can be useful for future experimental investigation on the title reaction.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Molecular Structure: THEOCHEM - Volume 897, Issues 1–3, 15 March 2009, Pages 1-5
نویسندگان
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