Title

Oxidized and reduced [2Fe-2S] clusters from an iron(I) synthon

Document Type

Article

Publication Date

7-27-2015

Abstract

© 2015 SBIC. Abstract Synthetic [2Fe-2S] clusters are often used to elucidate ligand effects on the reduction potentials and spectroscopy of natural electron-transfer sites, which can have anionic Cys ligands or neutral His ligands. Current synthetic routes to [2Fe-2S] clusters are limited in their feasibility with a range of supporting ligands. Here, we report a new synthetic route to synthetic [2Fe-2S] clusters, through oxidation of an iron(I) source with elemental sulfur. This method yields a neutral diketiminate-supported [2Fe-2S] cluster in the diiron(III)-oxidized form. The oxidized [2Fe-2S] cluster can be reduced to a mixed valent iron(II)-iron(III) compound. Both the diferric and reduced mixed valent clusters are characterized using X-ray crystallography, Mössbauer spectroscopy, EPR spectroscopy and cyclic voltammetry. The reduced compound is particularly interesting because its X-ray crystal structure shows a difference in Fe-S bond lengths to one of the iron atoms, consistent with valence localization. The valence localization is also evident from Mössbauer spectroscopy.

Publication Source (Journal or Book title)

Journal of Biological Inorganic Chemistry

First Page

875

Last Page

883

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