INFLUENCE OF BYSTANDER SUBSTITUENTS ON THE RATES OF 1,2-H AND 1,2-PH SHIFTS IN SINGLET AND TRIPLET CARBENES

Substituent effects at the migration origin on the rate of rearrangeme nt of several alkylchlorocarbenes have been studied at the B3LYP/6-311 G*//B3LYP/6-31G* level. Methyl, halo, and phenyl groups are found to accelerate 1,2-H shift rearrangements in the order Ph > Me > F > Cl > H. Methyl groups are also found to accelerate both singlet and triplet 1,2-Ph shifts in benzylchloro- and benzylcarbenes. A direct compariso n of the 1,2-H shift in methylchlorocarbene and the 1,2-Ph shift in be nzylchlorocarbene shows that the inherent migratory preference of a ph enyl group is greater than that of a hydrogen atom. Significant bystan der substituent effects are found, as originally proposed by Nickon.