Convenient syntheses of [IrCl(CS)(PPh(3))(2)] and a bis(thiocarbonyl) complex of iridium

Treating [IrCl(CO)(PPh(3))(2)] with ClC(=S)OR (R=C(6)H(4)Me-4) provides [IrCl2{C(=S)OR}(CO)(PPh(3))(2)], which reacts with NaBH4 to give [IrHCl{C(=S)OR}(CO)(PPh(3))(2)]. The aryloxide group is cleaved by HCl to give [IrHCl2(CS)(PPh(3))(2)], which is dehydrochlorinated by DBU to provide [IrCl(CS)(PPh(3))(2)] (overall yield for ''Ir(CO)''-->''Ir(CS)'' 75%). Treating [IrCl(CS)(PPh(3))(2)] with ClC(=S)SPh provides [IrCl2{C(=S)SPh}(CS)(PPh(3))(2)] (in equilibrium with [IrCl(eta(2)-SCSPh)(CS)(PPh(3))(2)]Cl) which reacts subsequently with I-2 or ICl to provide [IrCl2(CS)(2)(PPh(3))(2)]X (X=I-3, Cl). [Ir(CS(2)Ph)Cl-2(CO)(PPh(3))(2)], however, reacts with I-2 to provide [IrClI2(CS)(PPh(3))(2)]. Reaction of [IrHCl2(CS)(PPh(3))(2)] with CNC(6)H(3)Me(2)-2,6 does not proceed via migratory insertion but, rather, leads to reduction of iridium and formation of the salt [Ir(CNC(6)H(3)Me(2)-2,6)(2)(CS)(PPh(3))(2)]Cl.