Photolysis of [Fe 2 (CO) 6 (μ-CO)(μ-dppm)] (1) with SO 2 , CS 2 and ArNCS leads to the formation of [Fe 2 (CO) 6 (μ-SO 2 )(μ-dppm)] (2), [Fe 4 (CO) 1 0 (μ 3 -S)(μ-CS)(μ-dppm) 2 ] (3), [Fe 2 (CO) 3 (CNAr){μ-SC(NAr)C(O)S}(μ-dppm)] (4-5) and [Fe 2 (CO) 4 {μ-SC(N-p-tolyl)C(O)S}(μ-dppm)] (6), respectively. Complex 2 is a simple CO substitution product, while in 3 carbon-sulfur cleavage and coupling of diiron units has occurred. Dithiolate-bridged 4-6 also result from carbon-sulfur bond cleavage of one isothiocyanate and coupling of the sulfur with CO and a second isothiocyanate. Two isomers of complexes 3-6 are found and in thiolate-bridged 4-6 these interconvert as a result of inversion at the imine nitrogen, which has been monitored by VT NMR.