The dithiocarbonato metal complexes M(k²S,S-S₂CO)(k²P,P-dppf) {M= Ni, Pd, Pt; dppf=bis(diphenylphosphino)ferrocene} are obtained from the reaction of the metal(II) complexes [M(K²S,S-S₂-COEt)₂] with the dppf ligand or from the chloride substitution of M(k²P,P-dppf)Cl₂ by the O-ethyldithiocabonatoanion. These complexes are produced by C-O bond cleavage by the O-ethyldithiocarbonato anion present in solution. These new complexes have been characterized by UV-Vis, NMR, IR spectroscopy and elemental analysis. The structures of the three complexes were further confirmed by single-crystal X-ray diffraction analysis.

Vinyl selenocarboxylato iron complexes of the formula CpFe(CO)₂SeCOCH=C(R1)(R2) {R1 = H, R2 = Me, R1 = R2 = Me, R1 = H, R2 = CH=CHMe} are synthesized by the reaction of (l-Se)[CpFe(CO)₂]₂ with the corresponding vinyl acid chlorides ClCOCH=C(R1)(R2). Photolytic substitutionsof CpFe(CO)₂SeCOCH=CMe₂ with EPh₃ gave the monosubstituted complexes CpFe(CO)(EPh₃)-SeCOCH=CMe₂ (E = P, As, Sb) in good yields. The new complexes have been characterized by UV-Vis, IR,¹H-NMR, ¹³C{¹H}-NMR, ⁷⁷Se{¹H}-NMR, ³¹P{¹H}-NMR spectroscopy and elemental analysis. The solidstate structures of CpFe(CO)₂SeCOCH=CMe₂ and CpFe(CO) AsPh₃)SeCOCH=CMe₂ were determined by X-ray crystallography. The cyclic voltammetric measurements of CpFe(CO)₂SeCOCH=CMe₂ were recorded.

Half-sandwich iron thiocarboxylate complexes of the general formula CpFe(CO)₂-SCOCH=C(R^¢)(RR^¢¢){R^¢ = H, R^¢¢ = Me, R^¢ = R^¢¢ = Me, R^¢ = H, R^¢¢ = CH=CHMe}) are obtained from the reaction of (l-S_x)[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 complexesCpFe(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 andCpFe(CO)(PPh₃)SCOCH=CMe₂ were determined.