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.

O−CN bond cleavage of cyanates (ROCN) has been achieved at room temperature in the reaction of ROCN with a methyl Fe, Mo, or W complex. A mechanistic investigation involving DFT calculations revealed that silyl migration from Mo to the CN nitrogen gave an N-silylated η 2 -imidato Mo complex. This intermediate analogue was isolated and characterized by X-ray analysis. Catalytic O−CN bond cleavage was achieved using Cp(CO) 3 MoMe under thermal conditions.

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.

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