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Multiple electronic state mechanism for carboryne reaction with benzene: A DFT study
Author(s) -
Huo RuiPing,
Guo Lihui,
Zhang Fuqiang,
Zhang Xiang
Publication year - 2017
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25372
Subject(s) - cycloaddition , singlet state , benzene , reactivity (psychology) , chemistry , computational chemistry , product (mathematics) , reaction mechanism , open shell , electronic structure , stereochemistry , catalysis , organic chemistry , atomic physics , physics , mathematics , excited state , medicine , alternative medicine , geometry , pathology
The multiple electronic state mechanisms of the reaction of carboryne with benzene were investigated by M11 calculations. Mechanisms leading to [4 + 2] cycloaddition product P 4 + 2 , [2 + 2] cycloaddition product P 2 + 2 , CC insert product P C‐Cins and CH insert product P C‐Hins were considered. The barrier/stability to structural characteristics correlations revealed that, 1) [2 + 2] addition is a two‐step mechanism which exhibits three electronic state reactivity, and both the addition steps are controlled by the barriers on open‐shell singlet (OSS) potential energy surface (PES); 2) [4 + 2] product P 4 + 2 is a kinetic product on the experimental condition, and other products should be obtained under more harsher condition. The theoretical results well explain the experimental facts.