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Updated: Sep 27, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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Efficient Nicotinamide Adenine Dinucleotide Regeneration with a Rhodium-Carbene Catalyst and Isolation of a Hydride
Vinothkumar Ganesan1, Jennifer Juhyun Kim1, Jeongcheol Shin2
1Department of Chemistry, Chung-Ang University, Dongjak-gu, Seoul 06974, Republic of Korea.
Abstract:
Regeneration of nicotinamide adenine dinucleotide (NADH) has been the primary interest in the field of enzymatic transformation, especially associating oxidoreductases given the stoichiometric consumption. The synthesized carbene-ligated rhodium complex [(η5-Cp*)Rh(MDI)Cl]+ [Cp* = pentamethylcyclopentadienyl; MDI = 1,1'-methylenebis(3,3'-dimethylimidazolium)] acts as an exceptional catalyst in the reduction of NAD+ to NADH with a turnover frequency of 1730 h-1, which is over twice that of the higher catalytic activity of the commercially available catalyst [Cp*Rh(bpy)Cl]+ (bpy = 2,2'-bipyridine). Offsetting the contentious atmosphere currently taking place over the specific intermediate of the NADH regeneration, this study presents pivotal evidence of a metal hydride intermediate with a bis(carbene) ligand: a stable form of the rhodium hydride intermediate, [(η5-Cp*)Rh(MDI)H]+, was isolated and fully characterized. This enables thorough insight into the possible mechanism and exact intermediate structure in the NAD+ reduction process.
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