caa a22 4500 605507643 CHVBK 20210128100633.0 cr unu---uuuuu 210128e20150701xx s 000 0 eng 10.1007/s00775-015-1272-4 doi (NATIONALLICENCE)springer-10.1007/s00775-015-1272-4 Oxidized and reduced [2Fe-2S] clusters from an iron(I) synthon [Elektronische Daten] [Megan Reesbeck, Meghan Rodriguez, William Brennessel, Brandon Mercado, David Vinyard, Patrick Holland] 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. Graphical abstract: SBIC, 2015 Iron-sulfur cluster nationallicence Mössbauer spectroscopy nationallicence Diketiminate nationallicence Model cluster nationallicence Mixed valence nationallicence Reesbeck Megan Department of Chemistry, Yale University, 225 Prospect Street, 06520, New Haven, CT, USA aut Rodriguez Meghan Department of Chemistry, University of Rochester, 120 Trustee Road, 14627, Rochester, NY, USA aut Brennessel William Department of Chemistry, University of Rochester, 120 Trustee Road, 14627, Rochester, NY, USA aut Mercado Brandon Department of Chemistry, Yale University, 225 Prospect Street, 06520, New Haven, CT, USA aut Vinyard David Department of Chemistry, Yale University, 225 Prospect Street, 06520, New Haven, CT, USA aut Holland Patrick Department of Chemistry, Yale University, 225 Prospect Street, 06520, New Haven, CT, USA aut JBIC Journal of Biological Inorganic Chemistry Springer Berlin Heidelberg 20/5(2015-07-01), 875-883 0949-8257 20:5<875 2015 20 775 https://doi.org/10.1007/s00775-015-1272-4 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00775-015-1272-4 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Reesbeck Megan Department of Chemistry, Yale University, 225 Prospect Street, 06520, New Haven, CT, USA aut NATIONALLICENCE 700 1- Rodriguez Meghan Department of Chemistry, University of Rochester, 120 Trustee Road, 14627, Rochester, NY, USA aut NATIONALLICENCE 700 1- Brennessel William Department of Chemistry, University of Rochester, 120 Trustee Road, 14627, Rochester, NY, USA aut NATIONALLICENCE 700 1- Mercado Brandon Department of Chemistry, Yale University, 225 Prospect Street, 06520, New Haven, CT, USA aut NATIONALLICENCE 700 1- Vinyard David Department of Chemistry, Yale University, 225 Prospect Street, 06520, New Haven, CT, USA aut NATIONALLICENCE 700 1- Holland Patrick Department of Chemistry, Yale University, 225 Prospect Street, 06520, New Haven, CT, USA aut NATIONALLICENCE 773 0- JBIC Journal of Biological Inorganic Chemistry Springer Berlin Heidelberg 20/5(2015-07-01), 875-883 0949-8257 20:5<875 2015 20 775