Department of Mechanical Engineering, University of Illinois at Chicago, 842 West Taylor Street, Chicago, Illinois 60607, USA.
J Phys Chem A. 2012 Feb 2;116(4):1183-90. doi: 10.1021/jp208368a. Epub 2012 Jan 19.
Recent theoretical investigations of the radical/π-bond addition between single-ring aromatic hydrocarbons highlight the importance of this category of reactions for the formation of PAH intermediates and soot. The present investigation extends the theory of the radical/π-bond addition reactions to the o-benzyne + cyclic C(5) hydrocarbons systems. The calculations, performed using the uB3LYP/6-311+G(d,p) method, have addressed the possible role of the reaction between o-benzyne and cyclopentadiene in the formation of indene through the fragmentation of the bicyclo intermediate benzonorbornadiene. The complex potential energy surface for the reaction between o-benzyne and cyclopentadienyl radical was also investigated. In this case, the formation of the bicyclo benzonorbornadienyl radical and its subsequent fragmentation to indenyl radical and acetylene is not the main reaction pathway, although it could be relevant at relatively high temperatures. At lower temperatures, the isomerization reactions, which lead to the formation of a variety of multiring compounds, are dominant.
最近对单环芳烃自由基/π键加成反应的理论研究强调了这类反应对于 PAH 中间体和炭黑形成的重要性。本研究将自由基/π键加成反应的理论扩展到邻苯乙炔+环状 C(5)碳氢化合物体系。使用 uB3LYP/6-311+G(d,p)方法进行的计算，解决了邻苯乙炔和环戊二烯之间的反应在通过双环中间体苯并降冰片二烯的断裂形成茚的过程中可能起的作用。还研究了邻苯乙炔和环戊二烯基自由基之间反应的复杂势能面。在这种情况下，双环苯并降冰片二烯基自由基的形成及其随后裂解为茚基自由基和乙炔并不是主要反应途径，尽管在相对较高的温度下可能相关。在较低的温度下，导致多种多环化合物形成的异构化反应占主导地位。
