Ruthenium(II) complexes bearing pyridine‐based tridentate and bidentate ligands: catalytic activity for transfer hydrogenation of aryl ketones

Abstract

Ru(II) complexes of the general formula [RuCl2(′′)(L)] (1: ′N = Nb, L = MeOH; 2: ′N = Nb, L = CH3CN; 3: ′N = Nd, L = CH3CN; 4: ′N = Np, L = CH3CN), [Ru(p‐cymene)(a–b)Cl]Cl (5a: N Na = 2,2′‐bipyridine; 5b: N Nb = 4,4′‐dimethyl–2,2′‐bipyridine), [Ru(′′)(a–b)Cl]Cl (6a: ′N = Nb, a = 2,2′‐bipyridine; 6b: ′N = Nb, b = 4,4′‐dimethyl‐2,2′‐bipyridine; 7a: ′N = Nd, a = 2,2′‐bipyridine; 7b: ′N = Nd, b = 4,4′‐dimethyl‐2,2′‐bipyridine; 8a: ′N = Np, a = 2,2′‐bipyridine; 8b: ′N = Np, b = 4,4′‐dimethyl‐2,2′‐bipyridine) and [Ru(′′)(a)Cl]BF4 (9a: ′N = Nb; a = 2,2′‐bipyridine) were synthesized from the corresponding [RuCl2(p‐cymene)]2 dimer, ′′ and a–b ligands. The compounds were characterized by elemental analysis, IR and NMR. Complex 9a was studied by X‐ray diffraction, confirming its cationic‐mononuclear [RuCl(bb)(a)]+ nature. The synthesized Ru(II) complexes (1–8) were employed as catalysts for the transfer hydrogenation of ketones to secondary alcohols in the presence of KOH using 2‐propanol as a hydrogen source at 82°C. The rates of the transfer hydrogenation reactions strongly depended on the type of and ancillary ligands. Copyright © 2012 John Wiley & Sons, Ltd.