Investigation of the potential of molybdenum(VI) hydrazido(2–) complexes as sources of nitrenium ions: cleavage of the N–N bond and incorporation of the β-nitrogen group into solvent molecules

Abstract

Photolysis or thermolysis of bis(N,N-dimethyldithiocarbamato)bis[N-alkyl-N-phenylhydrazido(2–)]molybdenum(VI) complexes in 1,1,2,2-tetrachloroethane results predominantly in transfer of the hydrazido group to the solvent with formation of dichloroacetohydrazides. A small amount of the corresponding dichloroacetamides are produced by N–N cleavage and N(R)Ph transfer. In contrast, the latter process dominates the reaction of dichlorobis(N,N-dimethyldithiocarbamato)mono-[N-alkyl-N-phenylhydrazido(2-)]molybdenum(VI) complexes with silver nitrate in alcohols occuring concomitantly with ring methoxylation and nitration and N-nitrosation. Neither transfer of N(R)Ph appears to involve free nitrenium ions.