Insertion reactions of CCl with NH_3,H_2O,and CH_4:a theoretical comparative study on reactivity of CCl and CH

摘要

The CCl insertion reactions with NH_3,H_2O,and CH_4 have been studied by means of ab initio molecular orbital calculations incorporating correlation with the second-order Moller-Plesset perturbation theory using the 6-31G(d),6-31G(d,p),and 6-311+G(d,p)basis sets.The calculation results indicate that the reaction paths for the three CCl insertion reactions are similar to those for the respective CH insertion reactions(previously studied)while the CCl radical is less reactive than the CH radical.It is suggested that,in the MO interaction pictures,the highest doubly occupied MO and the two π~*MOs of CCl act as the highest doubly occupied MO and the two carbon Pπ-orbitals of CH,respectively,and this suggestion could lead to the under-standing of the similarities between the CCl and CH insertion reaction paths and the lower insertion reactivity of the CCl radical.