Abstract
Novel bis(phosphine) pincer complexes of iridium based on ferrocene and ruthenocene have been synthesized. The reaction of 1,3-bis((di-tert-butylphosphino)methyl)metallocenes [t-BuP,CH,PM] (M = Fe, 10; M = Ru, 13) with [Ir(COE)2Cl]2 in refluxing toluene leads to the corresponding chloro-hydrido pincer complexes as a mixture of H-endo- (M = Fe, 11; M = Ru, 14) and H-exo-IrH(Cl)[t-BuP,C,PM] (M = Fe, 12; M = Ru, 15) isomers. Treatment of compounds 11, 12 and 14, 15 with NaH in hot cyclooctane generates corresponding dihydrido complexes IrH2[t-BuP,C,PM] (M = Fe, 6; M = Ru, 7). Reactivity of the chelated iridium atom in hydrido-iridium pincer complexes and oxidation centered at the iron atom of ferrocene-based pincer complexes were studied. Complexes H-exo-IrH(Cl)(CO)[t-BuP,C,PFe] (20), Ir(CO)[t-BuP,C,PFe] (21), and Ir(CO)[2,6-(tBu2PO)2C6H3] (30) were characterized by X-ray crystallography. On the basis of νCO values for carbonyl iridium derivatives, electronic characteristics of the corresponding fragments {I...
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