title: Hydrogen evolution from aliphatic alcohols and 1,4-selective hydrogenation of NAD+ catalyzed by a [C,N] and a [C,C] cyclometalated organoiridium complex at room temperature in water.
abstract: A [C,N] cyclometalated Ir complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(H(2)O)](2)SO(4) [1](2)·SO(4), was reduced by aliphatic alcohols to produce the corresponding hydride complex [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))-benzoate-κC(3))H](-)4 at room temperature in a basic aqueous solution (pH 13.6). Formation of the hydride complex 4 was confirmed by (1)H and (13)C NMR, ESI MS, and UV-vis spectra. The [C,N] cyclometalated Ir-hydride complex 4 reacts with proton to generate a stoichiometric amount of hydrogen when the pH was decreased to pH 0.8 by the addition of diluted sulfuric acid. Photoirradiation (λ > 330 nm) of an aqueous solution of the [C,N] cyclometalated Ir-hydride complex 4 resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex 5 with no byproduct. The complex 5 catalyzed hydrogen evolution from ethanol in a basic aqueous solution (pH 11.9) under ambient conditions. The 1,4-selective catalytic hydrogenation of β-nicotinamide adenine dinucleotide (NAD(+)) by ethanol was also made possible by the complex 1 to produce 1,4-dihydro-β-nicotinamide adenine dinucleotide (1,4-NADH) at room temperature. The overall catalytic mechanism of hydrogenation of NAD(+), accompanied by the oxidation of ethanol, was revealed on the basis of the kinetic analysis and detection of the reaction intermediates.
authors.affiliation: Department of Material and Life Science, Graduate School of Engineering, Osaka University, ALCA, Japan Science and Technology Agency, Suita, Japan.
authors.forename: Yuta
authors.initials: Y
authors.lastname: Maenaka
authors.forename: Tomoyoshi
authors.initials: T
authors.lastname: Suenobu
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006859:Hydrogen / Q000737:chemistry*; D006865:Hydrogenation; D007495:Iridium / Q000737:chemistry*; D015394:Molecular Structure; D009243:NAD / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism; D009942:Organometallic Compounds / Q000737:chemistry*; D013696:Temperature; D014867:Water / Q000737:chemistry
chemical_list: D000438:Alcohols; D009942:Organometallic Compounds; D014867:Water; D009243:NAD; D007495:Iridium; D006859:Hydrogen