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Cycle formation from acetylene addition on C4H3 radicals.

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Lories, Xavier [UCL] Vandooren, Jacques [UCL] Peeters, Daniel [UCL]

Various reactions following acetylene addition on i- and n-C(4)H(3) radicals are studied using a modified G3B3 method. For the addition of C(2)H(2) on n-C(4)H(3), the commonly admitted phenyl radical decomposition path of Madden and coworkers has been considered. In addition, several energetically competitive cyclisation steps are described for the first time. Data concerning addition to form non-cyclisable compounds are also provided. Addition on i-C(4)H(3) is extensively described including new cyclisation steps and hydrogen elimination reactions. The lowest energy path from n- or i-C(4)H(3) to a cyclic system goes through dehydro-fulvene radicals formation, which in the case of n-C(4)H(3) + C(2)H(2) is energetically competitive to the formation of the phenyl radical. Considering the degradation of the latter, the formation of 6-dehydrofulvene is energetically competitive as compared to the decomposition to ortho-benzyne + H, which is the assumed main degradation channel of the phenyl radical. Rate constants for all the steps considered in this work are obtained through the conventional transition state theory and provided at the end of the paper.

Document type Article de périodique (Journal article) – Journal Article
Publication date 2010
Language Anglais
Journal information "Physical chemistry chemical physics : PCCP" - Vol. 12, no. 15, p. 3762-71 (2010)
Peer reviewed yes
issn 1463-9076
e-issn 1463-9084
Affiliations UCL - SST/IMMC - Institute of Mechanics, Materials and Civil Engineering
UCL - SST/IMCN - Institute of Condensed Matter and Nanosciences
Keywords CISM ; CECI
Links
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Bibliographic reference Lories, Xavier ; Vandooren, Jacques ; Peeters, Daniel. Cycle formation from acetylene addition on C4H3 radicals.. In: Physical chemistry chemical physics : PCCP, Vol. 12, no. 15, p. 3762-71 (2010)
Permanent URL http://hdl.handle.net/2078.1/31312