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Conception et réactivité de nouveaux complexes de lanthanides et de cobalt contenant des ligands rédox-actifs : application aux réductions multi-électroniques

Valentin Guidal 1, 2
1 RICC - Reconnaissance Ionique et Chimie de Coordination
SYMMES - SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé : DRF/INAC/SYMMES
Abstract : The redox chemistry of lanthanide complexes is attracting increasing interest because of the potential of divalent lanthanide complexes to promote unusual redox chemistry. For example they are able to activate small molecules such as CO2 and N2 in mild conditions. Due to the unique coordination and bonding properties of the lanthanide ions, their compounds could provide an attractive alternative to transition metals for the catalytic transformation of small molecules. However, metal-based multi-electron processes remain uncommon in lanthanide chemistry especially in comparison with the d-block metals; the chemistry of low-valent lanthanides being dominated by single-electron transfers. In this context, the first aim of this project was to investigate the association of lanthanides with a redox-active ligand acting as an independent electron reservoir within the same molecule. Accordingly, we examined the use of highly π-delocalized Schiff base ligands to study the reductive chemistry of lanthanide ions. This led to the isolation of electron-rich complexes which are stabilized by storing two or four electrons on the ligands through the formation of C-C bonds. Interestingly, these C-C bonds can be cleaved by oxidizing agents and the electrons released can participate in multi-electron redox reactions. This process was observed within different tridentate and tetradentate Schiff-base ligand scaffolds, allowing a tuning of the properties of the compounds. The ability of these complexes to react with CO2 has been studied, which lead to the identification of some neodymium complexes capable of reducing CO2. The second part of this work was dedicated to the study of cobalt complexes bearing redox-active and highly π-delocalized Schiff base ligands able to store electrons through the formation of C-C bonds. Seminal studies on Schiff base complexes of cobalt had been carried out in the 1990's and they demonstrated the ability of these complexes to activate CO2. With the aim to identify the active species responsible for CO2 activation, we have revisited these systems and highlighted a redox-isomeric equilibrium between a Co(I) and a Co(II) complexes where the electron can be localized on the cobalt or on the ligand. We also investigated the parameters influencing this equilibrium. In particular we have investigated the effect of the ligand architecture on the redox reactivity of cobalt complexes. Such studies pave the way to the development of new complexes for the electrocatlytic reduction of CO2.
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Valentin Guidal. Conception et réactivité de nouveaux complexes de lanthanides et de cobalt contenant des ligands rédox-actifs : application aux réductions multi-électroniques. Chimie inorganique. Université de Grenoble, 2014. Français. ⟨NNT : 2014GRENV022⟩. ⟨tel-01415217⟩

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