dc.contributor.advisor | Meyer, Franc Prof. Dr. | |
dc.contributor.author | Stevens, Hendrik | |
dc.date.accessioned | 2020-06-12T11:51:09Z | |
dc.date.available | 2021-05-13T00:50:24Z | |
dc.date.issued | 2020-06-12 | |
dc.identifier.uri | http://hdl.handle.net/21.11130/00-1735-0000-0005-13DA-0 | |
dc.identifier.uri | http://dx.doi.org/10.53846/goediss-8031 | |
dc.identifier.uri | http://dx.doi.org/10.53846/goediss-8031 | |
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 | Mechanistic Investigations of Metal-Metal Cooperativity in Dinickel Complexes and Iron/Cobalt Prussian Blue Analogues | de |
dc.type | doctoralThesis | de |
dc.contributor.referee | Meyer, Franc Prof. Dr. | |
dc.date.examination | 2020-05-15 | |
dc.description.abstracteng | This 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.coReferee | Schneider, Sven Prof. Dr. | |
dc.subject.eng | Metal-Metal Cooperativity | de |
dc.subject.eng | Nickel Hydride Complexes | de |
dc.subject.eng | C-H Activation | de |
dc.subject.eng | Low-Valent Metal Centers | de |
dc.subject.eng | Preorganized Ligand Scaffold | de |
dc.subject.eng | Iron/Cobalt Prussian Blue Analogues | de |
dc.subject.eng | Charge-Transfer-Induced Spin Transition | de |
dc.subject.eng | Transient Absorption Spectroscopy | de |
dc.identifier.urn | urn:nbn:de:gbv:7-21.11130/00-1735-0000-0005-13DA-0-5 | |
dc.affiliation.institute | Fakultät für Chemie | de |
dc.subject.gokfull | Chemie (PPN62138352X) | de |
dc.description.embargoed | 2021-05-13 | |
dc.identifier.ppn | 1700545663 | |