Synthesis, X-ray crystal structure, and reactivity of the monomeric dithio- o-carboranyl iridium complex [Ir(η 5-C 5Me 5)(η 2-S 2C 2B 10H 10)

Abstract

The reaction between the pentamethylcyclopentadienyl complex [Cp*IrCl 2] 2 and the dilithium dithio- o-carborane salt, Li 2[S 2C 2B 10H 10] ( 1), in THF affords the o-carborane-substituted compound Cp*Ir(S 2C 2B 10H 10) ( 2) in good yield. The complex [Cp*Ir(S 2C 2B 10H 10)] ( 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 PMe 3, CNBu t, and CO yield the corresponding complexes [Cp*Ir(S 2C 2B 10H 10)(PMe 3)] ( 3), [Cp*Ir(S 2C 2B 10H 10)(CNBu t)] ( 4), and [Cp*Ir(S 2C 2B 10H 10)(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.