Redox interconversion between metal thiolate and disulfide compounds

Jiang, F. (2018)

Doctoral Thesis

In the last decade, the redox interconversion between metal thiolate and disulfide compounds has been extensively investigated for copper, but not for other transition metal ions. In this thesis, our investigations are described of the possibility to extend the metal thiolate/disulfide redox interconversion reactions to cobalt or iron compounds. A number of cobalt(II) disulfide and cobalt(III) thiolate compounds of different ligands and different anions are reported in this thesis. It was revealed that the anion of cobalt(II) salts, the structure of disulfide ligands, and the type of solvent influence the formation of either cobalt(II) disulfide or cobalt(III) thiolate compounds. However, a consistent trend cannot be provided to predict which of the species is generated. An important conclusion of this work is that the cobalt(II) disulfide to cobalt(III) thiolate interconversion reaction might be related to the ligand field strength of the ligand, and the binding strength and ligand field strength of the anions and solvent used. Apart from the cobalt compounds, two iron(II) disulfide compounds were reported in this thesis as well. However, so far we were not able to trigger the conversion of these compounds to their respective iron(III) thiolate compounds.

• Biomimetics
• Coordination chemistry
• Cobalt
• Iron
• Redox Interconversion
• Thiolate
• Disulfide
• Oxidation

• All authors: Jiang, F.
• Supervisor: Bouwman, E.; Fonseca Guerra, C.
• Committee: Overkleeft, H.S.; Koper, M.T.M.; Bruin, B. de; Mao, Z.
• Qualification: Doctor (dr.)
• Awarding Institution: Institute of Chemistry (LIC), Faculty of Science, Leiden University
• Date: 2018-12-07