REACTIONS OF THIOCARBAMOYL COMPOUNDS WITH VASKA COMPLEXES: MECHANISM AND STEREOCHEMISTRY

Article abstract of DOI:10.1016/S0022-328X(00)90628-4

Bis(dimethylthiocarbamoyl)sulfide, (Me2NCS)2S, reacts with (Ph3P)2MCOCl complexes giving ionic species 2-CSNMe2)(S2CNMe2)CO>X (M = Rh, Ir; X = Cl, PF6) as kinetic products.On standing in solution, 2-CSNMe2)(S2CNMe2)CO>Cl is slowly transformed into the thermodynamic product Ph3PRh(η²-CSNMe2)(S2CNMe2)Cl.The known reactions of Vaska-type complexes with Me2NCSCL to give 2-CSNMe2)COCl>Cl and trans-(Ph3P)2Rh(η²-CSNMe2)Cl2 probably follow a similar course. (PH3P)2RuNOCl reacts with (Me2NCS)2S and Me2NCSCl in the same way as (Ph3P)2IrCOCl, but reacts with (Me2NCS)2NPh to give 2-CSNMe2)NOCl>PF6.The mechanism and stereochemistry of these reactions are discussed.Reactions were monitored by NMR spectroscopy in an attempt to identify intermediate η¹-thiocarboxamido complexes, but no such species could be detected.