Kirillov, Alexander M.Guedes Da Silva, M. Fátima C.Martins, LuisaSousa, CatarinaPombeiro, ArmandoAlegria, Elisabete2012-03-132012-03-132010-04-05Kirilov A M, Alegria E C B A, Silva M F C G, Martins L M D R S, Sousa C, Pombeiro A J L.Synthesis, characterization and redox behaviour of benzoyldiazenido- and oxorhenium complexes bearing N,N- and S,S-type ligands. Inorganica Chimica Acta. ISSN: 0020-1693. Vol. 363, N.º 6 (2010), pp. 1269-1274.0020-1693http://hdl.handle.net/10400.21/1296The reactions of [ReCl2{eta(2)-N2C(O)Ph}(PPh3)(2)](1) with 2-aminopyrimidine (H(2)Npyrm), 2,2'-bipyridine (bpy) and tetraethylthiuram disulfide (tds), in MeOH upon reflux, lead to the new eta(1)-(benzoyldiazenido)-rhenium(III) complexes [ReCl{eta(1)-N2C(O)Ph}(HNpyrm)(PPh3)(2)](2)and [ReCl2{eta(1)-N2C(O)Ph}(bpy)(PPh3)] (3), and the known oxo(diethyldithiocarbamato)dirhenium(v)complex [Re2O2(mu O){Et2NC(S)S}(4)](4), respectively. The Et2NC(S)S ligands in 4 result from S-S bond rupture of tds molecules. The obtained compounds have been characterized by IR, H-1, P-31{H-1} and C-13{H-1} NMR spectroscopies, FAB(+)-MS, elemental and single-crystal X-ray diffraction (for 2 and 4)analyses. Complex 2 represents the first structurally characterized Re compound derived from 2-aminopyrimidine. Besides, the redox behaviour of 2-4 in CH2Cl2 solution has been studied by cyclic voltammetry, and the Lever electrochemical ligand parameter (E-L)has been estimated, for the first time, for HNpyrm. The electrochemical results are discussed in terms of electronic properties of the Re centres and the ligands.engRheniumBenzoyldiazenido complexesPyrimidine2,2'-BipyridineDithiocarbamateElectrochemistryMild peroxidative oxidationRhenium complexesCoordination-compoundsMolecular-structureCrystal-structuresCatalytic-activityChemistryCyclohexaneAcidCycloalkalinesjournal article