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Proton Coupled Electron Transfer at Heavy Metal Sites

dc.contributor.advisorSchneider, Sven Prof. Dr.
dc.contributor.authorDelony, Daniel
dc.publisherNiedersächsische Staats- und Universitätsbibliothek Göttingende
dc.titleProton Coupled Electron Transfer at Heavy Metal Sitesde
dc.contributor.refereeMeyer, Franc Prof. Dr.
dc.description.abstractengTerminal, late transition metal, oxo complexes are pivotal intermediates in oxygenation chemistry. This thesis describes the synthesis and full characterisation of an open-shell terminal oxo complex of iridium from the respective iridium(II) hydroxo complex by proton coupled electron transfer (PCET). Electronic examinations of the compound support high oxyl radical character and reactivity studies reveal nucleo- to ambiphilic character of the iridium oxo moiety. Calorimetric determination of the O-H bond dissociation free energy reveals a bond strength sufficient for the activation of C-H bonds. Additionally, computational analysis reveals a small thermochemical contribution of spin-orbit-coupling (SOC) on the O-H bond strength, even though SOC effects on thermochemistry are mostly assumed to be negligible in solution thermochemistry. The effect of SOC on heavy metal PCET chemistry is further investigated on the example of a rhenium(III) amine complex forming the corresponding rhenium(IV) amide. By combination of spectroscopy, magnetometry, isothermal titration calorimetry and high-level ab initio computations a large SOC effect of several kcal/mol on the PCET thermochemistry is
dc.contributor.coRefereeHolthausen, Max C. Prof. Dr.
dc.subject.engCoordination Chemistryde
dc.subject.engTerminal Iridium Oxode
dc.subject.engProton-Coupled Electron Transferde
dc.subject.engIridium Pincer Complexesde
dc.subject.engRhenium Pincer Complexesde
dc.affiliation.instituteFakultät für Chemiede
dc.subject.gokfullChemie  (PPN62138352X)de

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