Multiple electronic state mechanism for carboryne reaction with benzene: A DFT study |
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| Authors: | Rui‐Ping Huo Li‐hui Guo Fu‐qiang Zhang Xiang Zhang |
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| Affiliation: | 1. Department of Chemistry, Taiyuan Normal University, Taiyuan, China;2. School of Chemistry and Materials Science, Shanxi Normal University, Linfen, China |
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| Abstract: | The multiple electronic state mechanisms of the reaction of carboryne with benzene were investigated by M11 calculations. Mechanisms leading to [4 + 2] cycloaddition product P4 + 2 , [2 + 2] cycloaddition product P 2 + 2 , C? C insert product P C‐Cins and C? H 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. |
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| Keywords: | benzene carboryne mechanism multiple electronic state |
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