Two novel asymmetric azo-aliphatic compounds [(CH3)3CNNC(S(CH2) n S)C(O)CH3, n = 2 (5) and n = 3 (6)] have been synthesized via a tandem procedure. The reaction of 5 and 6 with Fe2(CO)9 affords three novel dinuclear iron complexes displaying C−S bond activation (5b, 5c, and 6c). 5b and 5c exhibit an unusual stereochemistry about the Fe2 unit, as revealed by X-ray diffraction analyses. Additionally, two alquildithiolate-bridged iron hexacarbonyl complexes (5a and 6a) were obtained as a result of a double C−S bond activation from 5 and 6, respectively. The structures of 5, 5b, and 5c were fully established by X-ray diffraction analyses.