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

Abstract

Half-sandwich iron thiocarboxylate complexes of the general formula CpFe(CO)2SCOCH=C(R′)(R″){R′ = H, R″ = Me, R′ = R″ = Me, R′ = H, R″ = CH=CHMe}) are obtained from the reaction of (µ-Sx)[CpFe(CO)2]2 (x = 1–5) with the vinyl acid chlorides ClCOCH=C(R′)(R″). The substitution reaction of CpFe(CO)2SCOCH=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, 1H-NMR, 13C{1H}-NMR, 31P{1H}-NMR spectroscopy and elemental analysis. The solid state structures and the cyclic voltammetric measurements of CpFe(CO)2SCOCH=CMe2 and CpFe(CO)(PPh3)SCOCH=CMe2 were determined. Half-sandwich iron thiocarboxylate complexes of the general formula CpFe(CO)2SCOCH=C(R′)(R″){R′ = H, R″ = Me, R′ = R″ = Me, R′ = H, R″ = CH=CHMe}) are obtained from the reaction of (µ-Sx)[CpFe(CO)2]2 (x = 1–5) with the vinyl acid chlorides ClCOCH=C(R′)(R″). The substitution reaction of CpFe(CO)2SCOCH=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, 1H-NMR, 13C{1H}-NMR, 31P{1H}-NMR spectroscopy and elemental analysis. The solid state structures and the cyclic voltammetric measurements of CpFe(CO)2SCOCH=CMe2 and CpFe(CO)(PPh3)SCOCH=CMe2 were determined.