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Model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer: Synthesis and photophysical properties
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2004 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 43, no 15, 4683-4692 p.Article in journal (Refereed) Published
Abstract [en]

A model of the iron hydrogenase active site with the structure [(mu-ADT)Fe-2(CO)(6)] (ADT = azadithiolate (S-CH2-NR-CH2-S), (2: R = 4-bromophenyl, 3: R = 4-iodophenyl)) has been assembled and covalently linked to a [Ru(terpy)(2)](2+) photosensitizer. This trinuclear complex 1 represents one synthetic step toward the realization of our concept of light-driven proton reduction. A rigid phenylacetylene tether has been incorporated as the linking unit in 1 in order to prolong the lifetime of the otherwise short-lived [Ru(terpy)(2)](2+) excited state. The success of this strategy is demonstrated by comparison of the photophysical properties of 1 and of two related ruthenium complexes bearing acetylenic terpyridine ligands, with those of [Ru(terpy)(2)](2+). IR and electrochemical studies reveal that the nitrogen heteroatom of the ADT bridge has a marked influence on the electronic properties of the [Fe-2(CO)(6)] core. Using the Rehm-Weller equation, the driving force for an electron transfer from the photoexcited *[Ru(terpy)(2)](2+) to the diiron site in 1 was calculated to be uphill by 0.59 eV. During the construction of the trinuclear complex 1, n-propylamine has been identified as a decarbonylation agent on the [(mu-ADT)Fe-2(CO)(6)] portion of the supermolecule. Following this procedure, the first azadithiolate-bridged dinuclear iron complex coordinated by a phosphine ligand [(mu-ADT)Fe-2(CO)(5)PPh3] (4, R = 4-bromophenyl) was synthesized.

Place, publisher, year, edition, pages
2004. Vol. 43, no 15, 4683-4692 p.
Keyword [en]
fe-only hydrogenase, mlct excited-states, diiron subsite, desulfovibrio-desulfuricans, electrochemical-behavior, bridging ligands, complexes, coordination, mechanism, delocalization
URN: urn:nbn:se:kth:diva-23600ISI: 000222846300027OAI: diva2:342299
QC 20100525Available from: 2010-08-10 Created: 2010-08-10Bibliographically approved

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