Photochemical reactions of Fe(CO)<SUB>5</SUB> with Fc=CCH in the presence of S-powder and CS<SUB>2</SUB>: synthesis and characterization of [{μ-SC(H)=C(Fc)S}(CO)<SUB>6</SUB>Fe<SUB>2</SUB>], [{μ-SC(O)C(H)=C(Fc)S}(CO)<SUB>6</SUB>Fe<SUB>2</SUB>]; cis-[μ-η<SUP>1</SUP>:η<SUP>2</SUP>:η<SUP>1</SUP>:η<SUP>1</SUP>- {C(Fc)=C(H)CS<SUB>2</SUB>C(H)=C(Fc)}(CO)<SUB>6</SUB>Fe<SUB>2</SUB>] and trans-[μ-η<SUP>1</SUP>:η<SUP>2</SUP>:η<SUP>1</SUP>:η<SUP>1</SUP>-{C(Fc)=C(H)CS<SUB>2</SUB>C(Fc)=C(H)}(CO)<SUB>6</SUB>Fe<SUB>2</SUB>]

Photolysis of a hexane solution containing Fe(CO)5, ferrocenylacetylene and S-powder under argon at −30 °C led to the formation of two different products: [{μ-SC(H)C(Fc)S}(CO)6Fe2] (1) and [{μ-SC(O)C(H)C(Fc)S}(CO)6Fe2] featuring new C-S, C-C, Fe-Fe and Fe-S bond formations. In presence of CS2, formation of cis-[μ-η1:η2:η1:η1-{C(Fc)=C(H)CS2C(H)=C(Fc)}(CO)6Fe2] (5) and trans-[μ-η1:η2:η1:η1-{C(Fc)=C(H)CS2C(Fc)=C(H)}(CO)6Fe2] (6) was observed, along with 1. All new compounds were characterized by IR and 1H and 13C NMR spectroscopy. Structures of 1, 2, 5 and 6 were established crystallographically