Mndo investigation of the 1,2-rearrangement of singlet carbenes and nitrenes

1,2-Rearrangement of substituted methylcarbenes, carbonylcarbenes, methyinitrenes and carbonyltrenes have been calculated for singlet states by MNDO. The alteration in the electronic structure along the reaction course has been investigated by calculation and analysis of the transformation matrices between the MO's of the educts and the transition states. Migratory aptitudes are discussed as well as factors by which they may be determined. The effect of substituents at different positions has been investigated and conformational influences are discussed. As far as experimental results exist, the calculated data agree very well and offer a detailed understanding for the reaction mechanism and substituent effects.