A new ruthenium(II) NAD (NAD = Nicotinamide Adenine Dinucleotide) type bis‐carbonyl complex, [Ru(bpy)(pbn)(CO)2]2+ [pbn = 2‐(pyridin‐2‐yl)benzo[b]‐1,5‐naphthyridine; bpy = 2,2'‐bipyridine] [1]2+, was successfully synthesized and fully characterized by single‐crystal X‐ray structural analysis, ESI‐MS, IR and NMR spectroscopy. Complex [1]2+ together with [Ru(bpy)(pbn)(CO)(COOH)]+ and/or [Ru(bpy)(pbn) (CO)(CO2)]0 complexes exist as equilibrium mixtures in aqueous solutions as evident from spectroscopic study. Chemical reduction of [1]2+ resulted the formation corresponding NADH form i.e., [Ru(bpy)(pbnHH)(CO)2]2+ (pbnHH = 2‐(pyridin‐2‐yl)‐5,10‐dihydrobenzo[b][1,5]naphthyridine) [1.HH]2+ as a two‐electron‐reduced species. The electrochemical behavior of complex [1]2+ in the presence of acid was investigated based on cyclic voltammetry analysis. A control potential electrolysis of [1]2+ afforded formate (HCOO‐) as the major product with a lesser amount of CO and H2, whereas that of [Ru(bpy)2(CO)2]2+ complex produced CO as the main product with a lesser amount of HCOO‐ and H2. The experimental results suggest that the selectivity of HCOO‐ over CO should be due to catalytic hydride transfer from the NADH‐type ligands of [1]2+ to CO2.
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