Air-Stable Coordinatively Unsaturated Ruthenium(II) Complex for Ligand Binding and Catalytic Transfer Hydrogenation of Ketones from Ethanol.

Abstract

Coordinatively unsaturated complexes are interesting from a fundamental level for their formally empty coordination site and, in particular, from a catalytic perspective as they provide opportunities for substrate binding and transformation. Here, we describe the synthesis of a novel underligated ruthenium complex [Ru(cym)(N,N')]+, 3, featuring an amide-functionalized pyridylidene amide (PYA) as the N,N'-bidentate coordinating ligand. In contrast to previously investigated underligated complexes, complex 3 offers potential for dynamic modifications, thanks to the flexible donor properties of the PYA ligand. Specifically, they allow both for stabilizing the formally underligated metal center in complex 3 through nitrogen π-donation and for facilitating through π-acidic bonding properties the coordination of a further ligand L to the ruthenium center to yield the formal 18 e- complexes [Ru(cym)(N,N')(L)]+ (4: L = P(OMe)3; 5: L = PPh3; 6: L = N-methylimidazole; 7: L = pyridine) and neutral complex [RuCl(cym)(N,N')] 8. Analysis by 1H NMR and UV-vis spectroscopies reveals an increasing Ru-L bond strength along the sequence pyridine <1-methylimidazole < PPh3 < P(OMe)3 with binding constants varying over 3 orders of magnitude with log(Keq) values between 2.8 and 5.7. The flexibility of the Ru(PYA) unit and the ensuing accessibility of saturated and unsaturated species with one and the same ligand are attractive from a fundamental point of view and also for catalytic applications, as catalytic transformations rely on the availability of transiently vacant coordination sites. Thus, while complex 3 does not form stable adducts with O-donors such as ketones or alcohols, it transiently binds these species, as evidenced by the considerable catalytic activity in the transfer hydrogenation of ketones. Notably, and as one of only a few catalysts, complex 3 is compatible with EtOH as a hydrogen source. Complex 3 shows excellent performance in the transfer hydrogenation of pyridyl-containing substrates, in agreement with the poor coordination strength of this functional group to the ruthenium center in 3.