Vinylic-thiocarboxylate complexes of iron: synthesis, characterization and reactions

Half-sandwich iron thiocarboxylate complexes of the general formula CpFe(CO)(2)SCOCH=C(R ')(R ''){R ' = H, R '' = Me, R ' = R '' = Me, R ' = H, R '' = CH=CHMe}) are obtained from the reaction of (mu-S-x)[CpFe(CO)(2)](2) (x = 1-5) with the vinyl acid chlorides ClCOCH=C(R ')(R ''). The substitution reaction of CpFe(CO)(2)SCOCH=C(R)Me with EPh3 produced the monosubstituted complexes CpFe(CO)(EPh3)SCOCH=C(R)Me (R = Me, E = P, R = H, E = As, Sb). All the new complexes have been characterized by UV-Vis, IR, H-1-NMR, C-13{H-1}-NMR, P-31{H-1}-NMR spectroscopy and elemental analysis. The solid state structures and the cyclic voltammetric measurements of CpFe(CO)(2)SCOCH=CMe2 and CpFe(CO)(PPh3)SCOCH=CMe2 were determined. Graphic abstract Half-sandwich iron thiocarboxylate complexes of the general formula CpFe(CO)(2)SCOCH=C(R ')(R ''){R ' = H, R '' = Me, R ' = R '' = Me, R ' = H, R '' = CH=CHMe}) are obtained from the reaction of (mu-S-x)[CpFe(CO)(2)](2) (x = 1-5) with the vinyl acid chlorides ClCOCH=C(R ')(R ''). The substitution reaction of CpFe(CO)(2)SCOCH=C(R)Me with EPh3 produced the monosubstituted complexes CpFe(CO)(EPh3)SCOCH=C(R)Me (R = Me, E = P, R = H, E = As, Sb). All the new complexes have been characterized by UV-Vis, IR, H-1-NMR, C-13{H-1}-NMR, P-31{H-1}-NMR spectroscopy and elemental analysis. The solid state structures and the cyclic voltammetric measurements of CpFe(CO)(2)SCOCH=CMe2 and CpFe(CO)(PPh3)SCOCH=CMe2 were determined.