181028-50-2Relevant academic research and scientific papers
Convenient syntheses of [IrCl(CS)(PPh3)2] and a Bis(thiocarbonyl) complex of iridium
Hill, Anthony F.,Wilton-Ely, James D. E. T.
, p. 3791 - 3797 (2008/10/08)
Treating [IrCl(CO)(PPh3)2] with ClC(=S)OR (R = C6H4Me-4) provides [IrCl2{C(=S)OR}-(CO)(PPh3)2], which reacts with NaBH4 to give [IrHCl{C(=S)OR}(CO)(PPh3)2]. The aryloxide group is cleaved by HCl to give [IrHCl2(CS)(PPh3)2], which is dehydrochlorinated by DBU to provide [IrCl(CS)(PPh3)2] (overall yield for Ir(CO) → Ir(CS) 75%). Treating [IrCl(CS)-(PPH3)2] with ClC(=S)SPh provides [IrCl2{C(=S)SPh}(CS)(PPH3)2] (in equilibrium with [IrCl-(η2-SCSPh)(CS)(PPH3)2]Cl) which reacts subsequently with I2 or ICl to provide [IrCl2(CS)2-(PPH3)2]X (X = I3, Cl). [Ir(CS2Ph)Cl2(CO)(PPH3)2], however, reacts with I2 to provide [IrClI2(CS)(PPH3)2]. Reaction of [IrHCl2(CS)(PPH3)2] with CNC6H3Me2-2,6 does not proceed via migratory insertion but, rather, leads to reduction of iridium and formation of the salt [Ir(CNC6H3Me2-2,6)2(CS)(PPH 3)2]Cl. ? Dedicated to Professor Max Herberhold on the occasion of his 60th birthday.
