A new route to diiron bis(µ-thiocarbene) complexes: molecular structure of [{Fe{µ-C(CN)SMe](cp)}2](cp =η-C5H5) containing the unusually folded six-membered metallacycle Fe2C2S2

Abstract

The bis(µ-thiocarbene)[(cp)(OC)Fe{µC(CN)SMe}{µ-C([graphic omitted]e(cp)](X = H or CN; cp =µ-C₅H₅) and all the intermediate species obtained from the thiocarbyne derivative cis-[Fe₂(µ-CS){µ-C(SMe)}(CO)₂(cp)₂]-[SO₃CF₃]viaµ-C stereoselective addition of X^–, photochemical formation of [(cp)[graphic omitted]Me)X}(µ-CS)Fe-(CO)(cp)] followed by stepwise addition of MeSO₃CF₃ and (NBu₄ⁿ)CN at the bridging CS group have been prepared and characterized. Attempts to obtain the bis(µ-thiocarbene)[{Fe[µ-C(CN)SMe](CO)(cp)}₂] failed. The crystal structure of [{[graphic omitted]Me](cp)}₂] which demonstrates the presence of two doubly bridging thiocarbene groups has been determined. The results show that bis(µ-thiocarbene) derivatives are stable when at least one of the ligands acta as a double bridge via a S–Fe bond.