Electronic transfers in lanthanides complexes : from the electronic structure to the reactivity

Abstract : Understanding biological reactions require the use of molecules that can transfer electrons selectively and stabilise key intermediates. This work is interested into the design and the reactivity of divalent lanthanides that possess this kind of property.Firstly, organic molecules, i.e. phenanthroline and benzophenone, were reduced by samarium complexes. The thermodynamic data obtained for phenanthroline reduction was used to perform a benchmark study on different density functionals. TDDFT and CASSCF methods were then used to understand the electronic structure of the complexes and compared to the UV-visible spectrum of the molecules.Then, benzophenone ketyl and phenanthroline radicals have been used to perform radical reactions. Reactions with tempo led to already observed sterically induced reduction which mechanism was investigated. The competition between phenanthroline and benzophenone led to Minisci couplings that were never described with lanthanide complexes.Finally, the electron was transferred to organometallic species containing palladium via a bridge N-heterocycle ligand. Two of such species were compared towards the stabilisation of palladium at the IVth oxidation state. The importance of the ligand was further assessed by a combination of DFT and CASSCF calculations showing that certain ligands enabled a more direct transfer towards the palladium centre.
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Arnaud Jaoul. Electronic transfers in lanthanides complexes : from the electronic structure to the reactivity. Theoretical and/or physical chemistry. Université Paris-Saclay, 2017. English. ⟨NNT : 2017SACLX043⟩. ⟨tel-01637803⟩

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