LAUSR

Abstract Treatment of [ReOCl2{N(Ph2PO)2}(PPh3)] with one equivalent of sodium dialkyldithiocarbamate R2NCS2Na (R = Me, Et, iPr) in a mixed solvent of chloroform and methanol afforded the corresponding oxorhenium(V) complexes [ReOCl{N(Ph2PO)2}(S2CNMe2)]·CH2Cl2 (1), [ReOCl{N(Ph2PO)2}(S2CNEt2)] (2) and [ReOCl{N(Ph2PO)2}(S2CNiPr2)] (3). Reactions of [ReOCl3(PPh3)2] with an equimolar amount of iPr2NCS2Na or an excess of Et2NCS2Na in a mixed solvent of chloroform and methanol produced a mononuclear oxorhenium(V) complex [ReOCl2(S2CNiPr2)(PPh3)] (4) and a dinuclear oxorhenium(V) complex [Re2O3(S2CNEt2)4] (5, Tisley et al. in Inorg. Nucl. Chem. Lett. 7:523–526, 1971, Fletcher et al. in J. Chem. Soc., Dalton Trans. 10:1073–1078, 1972), respectively. These oxorhenium(V) complexes were characterized by infrared and ultraviolet spectroscopies, the crystal structures of complexes 1–5 have been determined by X-ray crystallography, and the electrochemical properties of new complexes 1–4 were also investigated.