title: Oxidation of diiron and triiron sulfurdithiolato complexes: mimics for the active site of [FeFe]-hydrogenase.
abstract: The oxidation of the hexacarbonyl(1,3-dithiolato-S,S')diiron complexes 4a-4c with varying amounts of dimethyldioxirane (DMD) was systematically studied. The chemoselectivity of the oxidation products depended upon the substituent R (R=H, Me, 1/2 (CH2)(5)). For R=H, four oxidation products, 6a-6d, have been obtained. In the case of R=Me, three products, 7a-7c, were formed, and for R=1/2 (CH2)(5), only complex 8 was observed. These observations are due to steric and electronic effects caused by the substituent R. Additionally, oxidation of the triiron complex 5 with DMD was performed to yield the products 9a and 9b. X-Ray diffraction analyses were performed for 6a-6d, 7a, and 7c, as well as for 9a and 9b. The electronic properties were determined by density-functional theory (DFT) calculations.
authors.affiliation: Friedrich-Schiller-Universität Jena, Institut für Anorganische und Analytische Chemie, August-Bebel-Strasse 2, D-07743 Jena (phone: +49-3641-948160).
authors.forename: Jochen
authors.initials: J
authors.lastname: Windhager
authors.affiliation: Friedrich-Schiller-Universität Jena, Institut für Anorganische und Analytische Chemie, August-Bebel-Strasse 2, D-07743 Jena (phone: +49-3641-948160).
authors.forename: Raphael A
authors.initials: RA
authors.lastname: Seidel
authors.affiliation: Friedrich-Schiller-Universität Jena, Institut für Anorganische und Analytische Chemie, August-Bebel-Strasse 2, D-07743 Jena (phone: +49-3641-948160).
authors.forename: Ulf-Peter
authors.initials: UP
authors.lastname: Apfel
authors.affiliation: Friedrich-Schiller-Universität Jena, Institut für Anorganische und Analytische Chemie, August-Bebel-Strasse 2, D-07743 Jena (phone: +49-3641-948160).
authors.forename: Helmar
authors.initials: H
authors.lastname: Görls
authors.affiliation: Ruprecht-Karls-Universität Heidelberg, Anorganisch-Chemisches Institut, Im Neuenheimer Feld 270, D-69120 Heidelberg (fax: +49-6221-546617).
authors.forename: Gerald
authors.initials: G
authors.lastname: Linti
authors.affiliation: Friedrich-Schiller-Universität Jena, Institut für Anorganische und Analytische Chemie, August-Bebel-Strasse 2, D-07743 Jena (phone: +49-3641-948160).
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Weigand
mesh_terms: D001665:Binding Sites; D018360:Crystallography, X-Ray; D006864:Hydrogenase / Q000737:chemistry*; D058085:Iron Compounds / Q000138:chemical synthesis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013457:Sulfur Compounds / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: D058085:Iron Compounds; D013457:Sulfur Compounds; D006864:Hydrogenase