Oxidation of diiron and triiron sulfurdithiolato complexes: mimics for the active site of [FeFe]-hydrogenase |
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Authors: | Windhager Jochen Seidel Raphael A Apfel Ulf-Peter Görls Helmar Linti Gerald Weigand Wolfgang |
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Affiliation: | 1. Friedrich‐Schiller‐Universit?t Jena, Institut für Anorganische und Analytische Chemie, August‐Bebel‐Strasse 2, D‐07743 Jena (phone: +49‐3641‐948160);2. Ruprecht‐Karls‐Universit?t Heidelberg, Anorganisch‐Chemisches Institut, Im Neuenheimer Feld 270, D‐69120 Heidelberg (fax: +49‐6221‐546617) |
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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. |
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Keywords: | Iron complexes Cluster compounds [FeFe]‐Hydrogenase Sulfur dithiolato complexes Oxidation X‐Ray crystallography Density‐functional theory (DFT) |
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