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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

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
Authors
Maenaka Y.Suenobu T.Fukuzumi S.
Ewha Authors
Shunichi Fukuzumi
SCOPUS Author ID
Shunichi Fukuzumiscopus
Issue Date
2012
Journal Title
Journal of the American Chemical Society
ISSN
0002-7863JCR Link
Citation
vol. 134, no. 22, pp. 9417 - 9427
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
A [C,N] cyclometalated Ir complex, [Ir III(Cp*)(4-(1H- pyrazol-1-yl-κN 2)benzoic acid-κC 3)(H 2O)] 2SO 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 1H and 13C 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. © 2012 American Chemical Society.
DOI
10.1021/ja302788c
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자연과학대학 > 화학·나노과학전공 > Journal papers
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