Bioinspired Dinuclear Copper Complexes for Small Molecule Activation

Spyra, Can-Jerome

dc.contributor.advisor	Meyer, Franc Prof. Dr.
dc.contributor.author	Spyra, Can-Jerome
dc.date.accessioned	2021-09-06T11:34:14Z
dc.date.available	2022-07-25T00:50:12Z
dc.date.issued	2021-09-06
dc.identifier.uri	http://hdl.handle.net/21.11130/00-1735-0000-0008-58FC-A
dc.identifier.uri	http://dx.doi.org/10.53846/goediss-8804
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	Bioinspired Dinuclear Copper Complexes for Small Molecule Activation	de
dc.type	doctoralThesis	de
dc.contributor.referee	Meyer, Franc Prof. Dr.
dc.date.examination	2021-07-27
dc.description.abstracteng	This thesis focuses on the activation of small molecules by dinuclear copper complexes. Initially, isolation of copper/oxygen intermediates on the basis of a non-symmetric pyrazolate/tacn scaffold was investigated. The employed ligand scaffold enforces a Cu-O-O-Cu torsion angle within the dinuclear peroxo complex close to 90°, making it a relevant model complex for the proposed intermediate along the trajectory of dioxygen binding at type III copper proteins. Further, interconversion of this non-symmetric peroxo complex to the hydroperoxo and superoxo intermediate was studied by UV/Vis spectroscopy. Elaboration of the respective binding motifs was done via Resonance Raman and EPR Spectroscopy as well as X-Ray diffraction. The determination of sought-after thermodynamic parameters, such as the pKa value of the Cu2OOH motif as well as the peroxo/superoxo redox potential could be determined by UV/Vis titration experiments and Cyclic Voltammetry measurements. On this basis the bond dissociation free energy of the hydroperoxo complex was derived and kinetic studies of the superoxo complex with TEMPO-H towards hydrogen atom transfer was investigated in detail. Thus, the isolated copper/oxygen complexes and their transformations completes the series of prior reported symmetrical pyrazolate/tacn copper/oxygen intermediates and demonstrates the gradual impact of ligand design on electronic properties of the respective complexes. Further isolation of a symmetric nitrosyl dicopper(II) complex on the basis of a pyrazolate/tacn scaffold was investigated, revealing fast conversion to the respective peroxo complex upon treatment with KO2. The nitrosyl complex further shows fast transformation to the respective dicopper(I) precursor upon chemical or electrochemical reduction.	de
dc.contributor.coReferee	Siewert, Inke Prof. Dr.
dc.subject.eng	Small Molecule Activation	de
dc.subject.eng	Bioinspired Model Complexes	de
dc.subject.eng	Copper Complexes	de
dc.subject.eng	Dioxygen Activation	de
dc.subject.eng	UV/Vis Spectroscopy	de
dc.subject.eng	Resonance Raman Spectroscopy	de
dc.subject.eng	Hydrogen Atom Transfer	de
dc.subject.eng	Bond Dissociation Free Energy	de
dc.subject.eng	EPR Spectroscopy	de
dc.identifier.urn	urn:nbn:de:gbv:7-21.11130/00-1735-0000-0008-58FC-A-8
dc.affiliation.institute	Fakultät für Chemie	de
dc.subject.gokfull	Chemie (PPN62138352X)	de
dc.description.embargoed	2022-07-25
dc.identifier.ppn	1769509208

Dateien

Name:Can-Jerome_Spyra_Dissertation.pdf

Größe:7.759Mb

Format:PDF

Beschreibung:Dissertation

Öffnen

Name:: Can-Jerome_Spyra_Dissertation.pdf
Größe:: 7.759Mb
Format:: PDF
Beschreibung:: Dissertation

Öffnen

Das Dokument erscheint in:

Fakultät für Chemie (inkl. GAUSS) [702]

Zur Kurzanzeige