title: Correlation between the Structure and Catalytic Activity of [Cp*Rh(Substituted Bipyridine)] Complexes for NADH Regeneration.
abstract: A series of water-soluble half-sandwich [Cp*RhIII(N^N)Cl]+(Cp* = pentamethylcyclopentadiene, N^N-substituted 2,2'-bipyridine) complexes containing electron-donating substituents around the 2,2'-bipyridyl ligand were synthesized and fully characterized for the regioselective reduction of nicotinamide coenzyme (NAD+). The influence of the positional effect of the substituents on the structural, electrochemical, and catalytic properties of the catalyst was systematically studied in detail. The catalytic efficiency of the substituted bipyridine Cp*RhIIIcomplexes are inversely correlated with their redox potentials. The 5,5'-substituted bipyridine Cp*RhIIIcomplex, which had the lowest reduction potential, most effectively regenerated NADH with a turnover frequency of 1100 h-1. Detailed kinetic studies on the generation of intermediate(s) provide valuable mechanistic insight into this catalytic cycle and help to direct the future design strategy of corresponding catalysts.
authors.affiliation: Department of Bio & Nano Chemistry, College of Natural Sciences, Kookmin University , 861-1 Jeoungnung-dong, Seongbuk-gu, Seoul 136-702, Republic of Korea.
authors.forename: Vinothkumar
authors.initials: V
authors.lastname: Ganesan
authors.affiliation: Department of Bio & Nano Chemistry, College of Natural Sciences, Kookmin University , 861-1 Jeoungnung-dong, Seongbuk-gu, Seoul 136-702, Republic of Korea.
authors.forename: Dharmalingam
authors.initials: D
authors.lastname: Sivanesan
authors.affiliation: Department of Bio & Nano Chemistry, College of Natural Sciences, Kookmin University , 861-1 Jeoungnung-dong, Seongbuk-gu, Seoul 136-702, Republic of Korea.
authors.forename: Sungho
authors.identifier: http://orcid.org/0000-0003-4521-2958
authors.initials: S
authors.lastname: Yoon
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D003517:Cyclopentanes / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009243:NAD / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: C550293:1,2,3,4,5-pentamethyl-cyclopentadiene; D003517:Cyclopentanes; D008024:Ligands; D009942:Organometallic Compounds; D009243:NAD; D015082:2,2'-Dipyridyl; D012238:Rhodium