N-CN bond cleavage of cyanamides (R2N-CN) has been attained at room temperature in the reaction of R2N-CN with Cp(CO)(2)Fe(SiEt3). 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.