Persistent URL of this record https://hdl.handle.net/1887/3421554
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Reactivity of cobalt(II)-dichalcogenide complexes: correlation between redox conversion and ligand-field strength
Finally, we have come up with several conclusions about the redox-conversion reactions of the cobalt(II)...Show moreThe redox-conversion reaction of metal-disulfide and metal-thiolate complexes are important, as they may shed light on electron-transfer reactions that often occur in Nature. Despite their importance, very few examples have been reported. In addition to that, there is a limited understanding of how the coordination environment of the metal ion affects this reaction. In this thesis, our investigation was set based on the ligand-field theory to determine its correlation with the redox-conversion reactions in cobalt-based systems. Our experiments revealed that using an exogenous ligand with a strong ligand-field character may induce the redox conversion from cobalt(II)-disulfide complexes to cobalt(III)-thiolate complexes. Using this knowledge, the possibility of the redox-conversion reaction was also extended from cobalt(II)-diselenide to cobalt(III)-selenolate complexes.
Finally, we have come up with several conclusions about the redox-conversion reactions of the cobalt(II)-dichalcogenide complexes. It was revealed that the conversion is affected by the ligand-field strength of the dichalcogenide ligand. The smaller ligand-field strength can be counterbalanced with the introduction of the strong auxiliary ligand. Lastly, the cleanliness of the conversion depends on the magnitude of the overall ligand-field splitting energy of the complex.
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- All authors
- Marvelous, C.
- Supervisor
- Bouwman, E.; Fonseca Guerra, C.
- Committee
- Overkleeft, H.S.; Bonnet, S.A.; Bruin, B. de; Duboc, C.; Broere, D.L.J.
- Qualification
- Doctor (dr.)
- Awarding Institution
- Leiden Institute of Chemistry (LIC), Faculty of Science, Leiden University
- Date
- 2022-07-05