The Absolute Kinetics of Several Reactions of Substituted Diphenylcarbenes

Article abstract of DOI:10.1021/j100402a044

4,4'-dibromo-, 4-bromo-, 4,4'-dichloro-, 4-chloro-, 4-methyl-, 4,4'-dimethyl-, 4-phenyl-, 4-carbomethoxyl-, 4-cyano-, 4-cyano-4'-methyl-, and 4,4'-dimethyldiphenyldiazomethane were studied by laser flash photolysis.Excitation of the diazo compounds at 308 nm produced the corresponding diarylcarbenes.The kinetics of the reaction of the substituted carbenes with alkanes and methanol were examined.Hydrogen abstraction rates are largely insensitive to ring substitution, while the methanol reaction is accelerated considerably by p-methyl substitution and retarded by a para electron-withdrawing substituent.