Proton Coupled Electron Transfer at Heavy Metal Sites

Delony, Daniel

dc.contributor.advisor	Schneider, Sven Prof. Dr.
dc.contributor.author	Delony, Daniel
dc.date.accessioned	2021-01-14T12:31:41Z
dc.date.available	2021-01-14T12:31:41Z
dc.date.issued	2021-01-14
dc.identifier.uri	http://hdl.handle.net/21.11130/00-1735-0000-0005-1546-5
dc.identifier.uri	http://dx.doi.org/10.53846/goediss-8400
dc.identifier.uri	http://dx.doi.org/10.53846/goediss-8400
dc.language.iso	eng	de
dc.publisher	Niedersächsische Staats- und Universitätsbibliothek Göttingen	de
dc.rights.uri	http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject.ddc	540	de
dc.title	Proton Coupled Electron Transfer at Heavy Metal Sites	de
dc.type	doctoralThesis	de
dc.contributor.referee	Meyer, Franc Prof. Dr.
dc.date.examination	2020-12-10
dc.description.abstracteng	Terminal, 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 revealed.	de
dc.contributor.coReferee	Holthausen, Max C. Prof. Dr.
dc.subject.eng	Spin-Orbit-Coupling	de
dc.subject.eng	Coordination Chemistry	de
dc.subject.eng	Terminal Iridium Oxo	de
dc.subject.eng	Proton-Coupled Electron Transfer	de
dc.subject.eng	Iridium Pincer Complexes	de
dc.subject.eng	Benchmarking	de
dc.subject.eng	Rhenium Pincer Complexes	de
dc.identifier.urn	urn:nbn:de:gbv:7-21.11130/00-1735-0000-0005-1546-5-0
dc.affiliation.institute	Fakultät für Chemie	de
dc.subject.gokfull	Chemie (PPN62138352X)	de
dc.identifier.ppn	1744718601

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