Multiple electronic state mechanism for carboryne reaction with benzene: A DFT study

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} , 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.