Synthesis, X-ray crystal structure, and reactivity of the monomeric dithio-o-carboranyl iridium complex [Ir(η5-C5Me5)(η2-S2C2B10H10)]

The reaction between the pentamethylcyclopentadienyl complex [Cp*IrCl2](2) and the dilithium dithio-o-carborane salt, Li-2[S2C2B10H10] (1), in THF affords the o-carborane-substituted compound Cp*Ir(S2C2B10H10) (2) in good yield. The complex [Cp*Ir(S2C2B10H10)] (2) has been isolated and characterized by X-ray diffraction analysis which confirmed a coordinatively unsaturated mononuclear complex. Subsequent addition reactions of complex 2 with the nucleophiles PMe3, CNBut, and CO yield the corresponding complexes [Cp*Ir(S2C2B10H10)(PMe3)] (3), [Cp*Ir(S2C2B10H10)(CNBut)] (4), and [Cp*Ir(S2C2B10H10)(CO)] (5). All of these new compounds have been isolated in high yield and characterized by IR and NMR spectroscopy. The solid state structures of 3 and 5 were determined by single-crystal X-ray diffraction analysis, exhibiting a characteristic three-legged 'piano-stool' arrangement around the iridium metal center. (C) 1999 Elsevier Science S.A. All rights reserved.