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Synthesis, structur...
Synthesis, structures and electrochemical properties of nitro- and amino-functionalized diiron azadithiolates as active site models of Fe-only hydrogenases
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Liu, T. B. (author)
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Wang, M. (author)
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Shi, Z. (author)
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Cui, H. G. (author)
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Dong, W. B. (author)
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Chen, J. S. (author)
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Akermark, B. (author)
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Sun, Licheng C. (author)
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- 2004-07-28
- 2004
- English.
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In: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 10:18, s. 4474-4479
- Related links:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
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- Complex [{(mu-SCH2)(2)N(4-NO2C6H4)}Fe-2(CO)(6)] (4) was prepared by the reaction of the dianionic intermediate [(mu-S)(2)Fe-2(CO)(6)](2-) and N,N-bis(chloromethyl)-4-nitroaniline as a biomimetic model of the active site of Fe-only hydrogenase. The reduction of 4 by Pd-C/H-2 under a neutral condition afforded complex [{(mu-SCH2)(2)N(4-NH2C6H4)}Fe-2(CO)(6)] (5) in 67% yield. Both complexes were characterized by IR, H-1 and C-13 NMR spectroscopy and MS spectrometry. The molecular structure of 4, as determined by X-ray analysis, has a butterfly 2Fe2S core and the aryl group on the bridged-N atom slants to the Fe(2) site. Cyclic voltammograms of 4 and 5 were studied to evaluate their redox properties. It was found that complex 4 catalyzed electrochemical proton reduction in the presence of acetic acid. A plausible mechanism of the electrocatalytic proton reduction is discussed.
Keyword
- bioinorganic chemistry
- cluster compounds
- diiron azaditholate
- iron only hydrogenase
- redox chemistry
- iron hydrogenase
- desulfovibrio-desulfuricans
- complexes
- chemistry
- dinuclear
- exchange
- coordination
- photosensitizer
- evolution
- ligands
Publication and Content Type
- ref (subject category)
- art (subject category)
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