Reversible Hydride Generation and Release from the Ligand of [Ru(pbn)(bpy)2](PF6)2 Driven by a pbn‐Localized Redox Reaction

Electrochemical reduction of [Ru(pbn)(bpy)2]2+ (1, pbn=2-(2-pyridyl)benzo[b]-1,5-naphthyridine, bpy=2,2′-bipyridine) in an acidic solvent gives [Ru(pbnH2)(bpy)2]2+ (2), which releases the hydrogen as “hydride” (see scheme). This catalytic system reduces substrates (for example, acetone) with two electrons and protons from water, and thus operates in a similar way to the NAD+/NADH redox couple.