om700943w_si_002.cif (53.97 kB)

Increasing the Reactivity of Vaska’s Compound. Oxidative Addition of Chlorobenzene at Ambient Temperature

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posted on 10.03.2008, 00:00 by Christos Douvris, Christopher A. Reed
Silylium ion-like reagents, R3Siδ+(carboraneδ−), are successful where silver salts fail in abstracting chloride ion from IrCl(CO)(PPh3)2 in arene solvents. Replacement of chloride by a very weakly coordinating carborane anion such as CHB11H5Cl6 promotes unusually facile oxidative addition of chlorobenzene, giving the coordinatively unsaturated IrCl(CO)(C6H5)(PPh3)2]+ cation. Other arene solvents promote disproportionation with loss of a phosphine ligand to give labile Ir(I) cations of the type [Ir(arene)(CO)(PPh3)]+, having three latent vacant coordination sites.