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Protonation, electrochemical properties and molecular structures of halogen-functionalized diiron azadithiolate complexes related to the active site of iron-only hydrogenases
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2007 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, no 34, 3812-3819 p.Article in journal (Refereed) Published
Abstract [en]

Diiron complexes [{( mu-SCH2) 2NCH(2)C(6)H(4)X}{Fe( CO)(2)L}(2)] ( L = CO, X = 2-Br, 1; 2-F, 2; 3-Br, 3; L = PMe3, X = 2-Br, 4) were prepared as biomimetic models of the iron-only hydrogenase active site. The N-protonated species [ 1( NH)]+ClO4-, [ 2( NH)]+ClO4- and the mu-hydride diiron complex [ 4( FeHFe)]+PF6- were obtained in the presence of proton acids and well characterized. The protonation process of 4 was studied by in-situ IR and NMR spectroscopy, which suggests the formation of the diprotonated species [ 4( NH)( FeHFe)](2+) in the presence of an excess of proton acid. The molecular structures of 1, [ 1( NH)]+ClO4-, 4 and [ 4( FeHFe)]+PF6- were determined by X-ray crystallography. The single-crystal X-ray analysis reveals that an intramolecular H center dot center dot center dot Br contact ( 2.82 angstrom) in the crystalline state of [ 1( NH)]+ClO4-. In the presence of 1-6 equiv of the stronger acid HOTf, complex 1 is readily protonated on the bridged-N atom and can electrochemically catalyze the proton reduction at a relatively mild potential ( ca. -1.0 V). Complex 4 is also electrocatalytic active at -1.4 V in the presence of HOTf with formation of the mu-hydride diiron species.

Place, publisher, year, edition, pages
2007. no 34, 3812-3819 p.
Keyword [en]
desulfovibrio-desulfuricans, bridging ligand, model complexes, h-2 evolution, coordination, reduction, catalysis, relevant, hydride, cluster
Identifiers
URN: urn:nbn:se:kth:diva-16892DOI: 10.1039/b706178aISI: 000248917200011Scopus ID: 2-s2.0-34548064570OAI: oai:DiVA.org:kth-16892DiVA: diva2:334935
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved

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