Desulfurization of N,N-dimethylthioformamide by hydrosilane with the help of an iron complex. Isolation and characterization of an iron-carbene complex as an intermediate of C=double bond cleavage.

Desulfurization of N,N-dimethylthioformamide (Me(2)NCHS) by hydrosilane has been achieved under photo irradiation in the presence of a methyl iron complex. The reaction sequences have been proposed, in which silyl migration from Fe to S of thioformamide triggers the cleavage of a C=S bond to give a carbene-iron complex. This intermediate was isolated and characterized by X-ray analysis.

N-CN bond cleavage of cyanamides by a transition-metal complex.

N-CN bond cleavage of cyanamides (R(2)N-CN) has been attained at room temperature in the reaction of R(2)N-CN with Cp(CO)(2)Fe(SiEt(3)). The mechanistic investigation revealed that silyl migration from Fe to CN nitrogen of cyanamide gave an N-silylated eta(2)-amidino iron complex, which was isolated and characterized by X-ray analysis. Catalytic N-CN bond cleavage was also attained using a methyl molybdenum complex under thermal conditions.