The reaction of N-(3-methyl-2-thienylmethylidene)aniline with Fe 2 (CO) 9 under mild conditions in anhydrous benzene gives ironcarbonyl organometallic products 2b, 2c, 5, and an organic product 4c. Complexes 2b and 2c are cyclometalated diironhexacarbonyl isomers, in which the methyl group has migrated from β- to β'- and α'-carbon of the thienyl ring, respectively. Complex 5 is a triironnonacarbonyl cluster with an imidoyl ligand capped on the top of the three-iron plane and a hydrogen atom bridged to two irons. The organic product 4c is a hydrogenated product of the original Schiff base. Single crystals of 2c and 5 were subjected to the X-ray diffraction analysis and their structures thus confirmed.