Cationic π-carbon disulphide complexes of rhodium and iridium; thiocarbonyl complexes of iridium

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Abstract
The interaction of trans-chlorocarbonylbis(triphenylphosphine)iridium(I) with carbon disulphide and triphenylphosphine in methanol gives a deep violet solution which has been shown to contain the ion carbonyl-(π-carbon disulphide)tris(triphenylphosphine)iridium(III), [Ir(CO)(π-CS2)(PPh3)3]+. The tetraphenylborate salt has been isolated. Similar blue or green cationic species have been obtained from trans-IrCl(CS)(PPh3)2, trans-RhCl(CO)(PPh3)2, trans-RhCl(CS)(PPh3), RhCl(PPh3)3, and IrCl(PPh3)3. The relationship of such species to the formation of thiocarbonyl complexes is discussed. The thiocarbonyl complex trans-IrCl(CS)(PPh3)2 has been prepared, and the adducts IrCl(CS)(CO)(PPh3)2 and IrCl(CS)SO2(PPh3)2 and also the hydrido-species IrH(CS)(PPh3)3 have been obtained from it.