Theoretical Study on the Mechanism of the Cycloaddition Reaction between Alkylidene Carbene and Ethylene

Abstract

AbstractThe mechanism of cycloaddition reaction between singlet alkylidene carbene and ethylene has been investigated with second‐order Moller‐Plesset perturbation theory (MP2). By using 6–31G* basis, geometry optimization, vibrational analysis and energetics have been calculated for the involved stationary points on the potential energy surface. The results show that the title reaction has two major competition channels. An energy‐rich intermediate (INT) is firstly formed between alkylidene carbene and ethylene through a barrier‐free exothermic reaction of 63.62 kJ/mol, and the intermediate then isomerizes to a three‐membered ring product (Pl) and a four‐membered ring product (P2) via transition state TS1 and TS2, in which energy barriers are 47.00 and 51.02 kl/mol. respectively. PI is the main product.