Abstract
A series of iridium and rhodium complexes [M(COD)(PhPNHP)]Cl {M = Ir (1), Rh (2)}, [MH2Cl(PhPNHP)] {M = Ir (3), Rh (4)} and [IrH3(PhPNHP)] (6) supported by pincer ligand HN(CH2CH2PPh2)2 {PhPNHP} have been synthesized and characterized. All complexes were isolated in good yields. The iridium trihydride complex [IrH3(PhPNHP)] (6) was found to be an active catalyst for the hydrogenation of CO2 in 1 M aqueous KOH solution. It also acts as a catalyst for the base-free hydrogenation of carbonyl and imine substrates in MeOH. Under similar hydrogenation conditions, 2-cyclohexen-1-one undergoes solvent assisted tandem Michael addition-reduction mediated by bifunctional Lewis-acid-catalyst [IrH3(PhPNHP)] in ROH (R = Me, Et) at room temperature. The complexes 1, 3, 4, and 6 were characterized by X-ray crystallography. Extensive hydrogen bonding interactions NH⋯HIr (2.15 Å), NH⋯Cl (2.370 Å) were noted in the crystal structures of these complexes.
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