<> "The repository administrator has not yet configured an RDF license."^^ . <> . . "Experimentelle und theoretische Untersuchungen der Eigenschaften von hochvalenten Bispidin-Eisen(IV)-Oxo-Komplexen"^^ . "This thesis deals with the study of the properties of bispidine iron(IV)-oxo complexes.\r\nThese are biomimetic model compounds for non-heme iron enzymes.\r\nThe first part describes the thermal spin crossover behavior of the tetradentate bispidine\r\nligands’ iron(II) complexes. These compounds were precisely characterized using\r\nUV-vis-NIR and Mößbauer spectroscopy as well as Evans NMR spectroscopy and SQUID\r\nmeasurements. The tetradentate bispidine ligands’ iron(IV)-oxo complexes were\r\ncharacterized using UV-vis-NIR and Mößbauer spectroscopy. They were also analyzed\r\ncomputationally with DFT calculations. In addition, it was possible to characterize a high\r\nspin iron(IV)-oxo species by Mößbauer spectroscopy. This species’ electron transfer\r\nproperties were analyzed.\r\nThe second part of this study is about the photocatalytic generation of an iron(IV) oxo\r\nspecies with water as oxygen source. [RuII(bpy)3] 2+ was used as a photosensitizer. After\r\nirradiating it with visible light it was oxidized with [CoIII(NH3)5(MeCN)] 3+ to\r\n[RuIII(bpy)3] 3+, which catalytically generates in situ an iron(IV)-oxo species with water as\r\nsource of oxygen. This reaction is also interesting with regard to environmental issues as it\r\nseems promising to use solar energy to produce highly energetic species.\r\nThe third part of this study covers the redox properties of the pentadentate bispidine\r\nligands’ ferryl complexes when the redox inactive metal ion Sc3+ is present. The presence\r\nof Sc3+ shifts the redox potential of the ferryl complex to higher potentials. This effect can\r\nbe used to manipulate the electron transfer properties of the ferryl compound. This FeIV(O)-\r\nSc3+ complex can serve as a model compound for the Mn4CaO5 cluster in the\r\nphotosystem II.\r\nThe last part of this study is about the non heme iron-oxo-catalyzed methanogenesis. The\r\nferryl complexes of the tetra- and pentadentate bispidine ligands produce methane from\r\nmethionine and other thioethers. In the first step of the process, methionine is oxidized to\r\nmethionine sulfoxide. A bifurcation of the reaction pathway to a sulfone or methyl radical\r\nproduction marks the second step of the process. The generation of methyl radicals was\r\nconfirmed by spin trapping experiments. By way of detailed DFT calculations it was\r\npossible to shed light on the mechanism of methane formation in a highly oxidative\r\nenvironment."^^ . "2015" . . . . . . . "Kathrin Julia"^^ . "Benzing"^^ . "Kathrin Julia Benzing"^^ . . . . . . "Experimentelle und theoretische Untersuchungen der Eigenschaften von hochvalenten Bispidin-Eisen(IV)-Oxo-Komplexen (PDF)"^^ . . . "Dissertation_KathrinBenzing_2015.pdf"^^ . . . "Experimentelle und theoretische Untersuchungen der Eigenschaften von hochvalenten Bispidin-Eisen(IV)-Oxo-Komplexen (Other)"^^ . . . . . . "lightbox.jpg"^^ . . . "Experimentelle und theoretische Untersuchungen der Eigenschaften von hochvalenten Bispidin-Eisen(IV)-Oxo-Komplexen (Other)"^^ . . . . . . "preview.jpg"^^ . . . "Experimentelle und theoretische Untersuchungen der Eigenschaften von hochvalenten Bispidin-Eisen(IV)-Oxo-Komplexen (Other)"^^ . . . . . . "medium.jpg"^^ . . . "Experimentelle und theoretische Untersuchungen der Eigenschaften von hochvalenten Bispidin-Eisen(IV)-Oxo-Komplexen (Other)"^^ . . . . . . "small.jpg"^^ . . . "Experimentelle und theoretische Untersuchungen der Eigenschaften von hochvalenten Bispidin-Eisen(IV)-Oxo-Komplexen (Other)"^^ . . . . . . "indexcodes.txt"^^ . . "HTML Summary of #19687 \n\nExperimentelle und theoretische Untersuchungen der Eigenschaften von hochvalenten Bispidin-Eisen(IV)-Oxo-Komplexen\n\n" . "text/html" . . . "540 Chemie"@de . "540 Chemistry and allied sciences"@en . .