Xavier Lories1, Jacques Vandooren, Daniel Peeters. 1. Laboratoire de Chimie Quantique, Université catholique de Louvain, Département de Chimie, Bâtiment Lavoisier, Place Louis Pasteur, 1, B-1348 Louvain-la-Neuve, Belgium.
Abstract
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.
Various reactions following acetylene addition on i- and n-n class="Chemical">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.
Authors: Brant M Jones; Fangtong Zhang; Ralf I Kaiser; Adeel Jamal; Alexander M Mebel; Martin A Cordiner; Steven B Charnley Journal: Proc Natl Acad Sci U S A Date: 2010-12-27 Impact factor: 11.205