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Effect of the S-to-...
Effect of the S-to-S bridge on the redox properties and H-2 activation performance of diiron complexes related to the [FeFe]-hydrogenase active site
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Cheng, Minglun (author)
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Wang, Mei (author)
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Zheng, Dehua (author)
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- Sun, Licheng (author)
- KTH,Organisk kemi,Molekylär elektronik, CMD
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(creator_code:org_t)
- 2016
- 2016
- English.
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In: Dalton Transactions. - : ROYAL SOC CHEMISTRY. - 1477-9226 .- 1477-9234. ; 45:44, s. 17687-17696
- 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
Subject headings
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- Three biomimetic models of the [FeFe]-hydrogenase active site, namely diiron dithiolates of [(mu-edt){Fe(CO)(3)}{Fe(CO)(kappa(2)-PNP)}] (1, edt = ethane-1,2-dithiolate, PNP = Ph2PCH2N(nPr)CH2PPh2), [(mu bdtMe){Fe(CO)(3)}{Fe(CO)(kappa(2)-PNP)}] (2, bdtMe = 4-methylbenzene-1,2-dithiolate), and [(mu-adtBn){Fe(CO)(3)} {Fe(CO)(kappa(2)-PNP)}] (3, adtBn = N-benzyl-2-azapropane-1,3-dithiolate), were prepared and structurally characterized. These complexes feature the same PNP ligand but different S-to-S bridges. Influence of the S-to-S bridge on the electrochemical properties and chemical oxidation reactivity of 1-3 was studied by cyclic voltammetry and by in situ IR spectroscopy. The results reveal that the S-to-S bridge has a considerable effect on the oxidation reactivity of 1-3 and on the stability of in situ generated single-electron oxidized complexes, [1](+), [2](+), and [3](+). The performances of [1](+) and [2](+) for H-2 activation were explored in the presence of a mild chemical oxidant, while rapid decomposition of [3](+) thwarted the further study of this complex. Gratifyingly, 1 was found to be catalytically active, although in a low turnover number, for H-2 oxidation in the presence of excess mild oxidant and a proton trapper under 1 atm H-2 at room temperature.
Subject headings
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
Publication and Content Type
- ref (subject category)
- art (subject category)
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