Reactions of [(μ-RS)(μ-S){Fe2(CO)6}2(μ4-S)]− with acid chlorides and diacid chlorides. Crystal structure of (μ-PhCH2S)[μ-CH2C(Me)COS][Fe2(CO)6]2(μ4-S)

The reaction of anionic complexes [(μ-RS)(μ-S){Fe2(CO)6}2(μ4-S)]− (1) with acid chlorides R1COCl [R1=Me, Ph, PhCHCH, CH2C(Me)] gives S-acylated compounds (μ-RS)(μ-R1COS)[Fe2(CO)6]2(μ4-S) (2a–h). However, if R1 in R1COCl is an electron-withdrawing group such as EtO2C and p-O2NC6H4, the reaction produces [(μ-RS)Fe2(CO)6]2(μ4-S) (R=Ph (4)), [(μ-RS)Fe2(CO)6(μ4-S)]2Fe2(CO)6 (R=Ph (5a), tBu (5b)) and [(μ-RS)Fe2(CO)6]2(μ-S-S-μ) (R=tBu (6)). The same results were achieved in the reaction by use of diacid chlorides or SO2Cl2 instead of EtO2CCOCl and p-O2NC6H4COCl. The structure of complex (μ-PhCH2S)[μ-CH2C(Me)COS][Fe2(CO)6]2(μ4-S) (2d) was determined by single-crystal X-ray diffraction.