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Mechanistic Investigations of Metal-Metal Cooperativity in Dinickel Complexes and Iron/Cobalt Prussian Blue Analogues

dc.contributor.advisorMeyer, Franc Prof. Dr.
dc.contributor.authorStevens, Hendrik
dc.date.accessioned2020-06-12T11:51:09Z
dc.date.available2021-05-13T00:50:24Z
dc.date.issued2020-06-12
dc.identifier.urihttp://hdl.handle.net/21.11130/00-1735-0000-0005-13DA-0
dc.identifier.urihttp://dx.doi.org/10.53846/goediss-8031
dc.identifier.urihttp://dx.doi.org/10.53846/goediss-8031
dc.language.isoengde
dc.publisherNiedersächsische Staats- und Universitätsbibliothek Göttingende
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject.ddc540de
dc.titleMechanistic Investigations of Metal-Metal Cooperativity in Dinickel Complexes and Iron/Cobalt Prussian Blue Analoguesde
dc.typedoctoralThesisde
dc.contributor.refereeMeyer, Franc Prof. Dr.
dc.date.examination2020-05-15
dc.description.abstractengThis dissertation focuses on two polymetallic systems exhibiting two different phenomena of Metal-Metal Cooperativity in the form of intramolecular C-H(sp2) activation and Charge-Transfer-Induced Spin Transition (CTIST). The first system, a dinickel complex, utilizes a preorganized ligand scaffold of two β-diketiminato units bridged by pyrazole. The proximity of the two metal centers results in an intramolecular C-H activation of the ligand backbone and a hydride- and phenyl-ligation. This C-H activation was also found to be reversible by the addition of dihydrogen resulting in a nickel dihydride complex. Here, the mechanism of the C-H / H2 activation was investigated, and a Ni(I)Ni(I) intermediate undergoing oxidative addition was hypothesized supported by trapping experiments with deuterium gas and benzaldehyde. Furthermore, an effect of the alkali metal towards reactivity was investigated, wherein a second C-H activation going through a σ-bond metathesis was observed. Based on the knowledge about the system the reactivities towards other small molecules, such as N2, O2, CO and CO2 were investigated. Molecular Iron/Cobalt Prussian Analogues (Fe/Co PBAs) can exhibit an electron-transfer-coupled spin transition between a diamagnetic and paramagnetic state upon irradiation of light. Therefore, the second part of this dissertation focuses on the development of new dinuclear Fe/Co PBAs bearing tetrapyrazolyl lutidine ligands. A thermal-induced CTIST was not observed for the synthesized complexes and the paramagnetic state prevailed over the whole temperature range as concluded by magnetic susceptibility measurements. To investigate the mechanism of a photo-induced CTIST one of the dinuclear system and a literature-known tetranuclear benchmark system was investigated by time-resolved spectroscopy. Through time-trace analysis, two different mechanisms dependent on the magnetic ground state were hypothesized, with only one of them revolving around a spin-transition.de
dc.contributor.coRefereeSchneider, Sven Prof. Dr.
dc.subject.engMetal-Metal Cooperativityde
dc.subject.engNickel Hydride Complexesde
dc.subject.engC-H Activationde
dc.subject.engLow-Valent Metal Centersde
dc.subject.engPreorganized Ligand Scaffoldde
dc.subject.engIron/Cobalt Prussian Blue Analoguesde
dc.subject.engCharge-Transfer-Induced Spin Transitionde
dc.subject.engTransient Absorption Spectroscopyde
dc.identifier.urnurn:nbn:de:gbv:7-21.11130/00-1735-0000-0005-13DA-0-5
dc.affiliation.instituteFakultät für Chemiede
dc.subject.gokfullChemie  (PPN62138352X)de
dc.description.embargoed2021-05-13
dc.identifier.ppn1700545663


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