Synthèse et étude de ligands hydroxamates cycliques dérivés des sidérophores naturels pour la complexation sélective des actinides

Synthesis and investigation of cyclic hydroxamate ligands derived from natural siderophores for selective complexation of actinides

• Auteur / Autrice : Pawel Jewula
• Direction : Michel Meyer, Jean-Claude Chambron
• Type : Thèse de doctorat
• Discipline(s) : Chimie - physique
• Date : Soutenance le 25/09/2013
• Etablissement(s) : Dijon
• Ecole(s) doctorale(s) : École doctorale Carnot-Pasteur (Besançon ; Dijon ; 2012-....)
• Partenaire(s) de recherche : Laboratoire : Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB) (Dijon)
• Jury : Président / Présidente : Pierre Le Gendre
• Jury : Examinateurs / Examinatrices : Pascal Sonnet
• Jury : Rapporteur / Rapporteuse : Olivier Duval, Jean-Bernard Regnouf de Vains

Mots clés

Mots clés contrôlés

Complexes métalliques

Complexation

Actinides

Sidérophores

Synthèse (chimie)

Acides hydroxamiques

Mots clés libres

Pas de mots-clés en français

Cyclic hydroxamic acid

Alix[4]arene tetrapodal receptor

Iron(III)

Gallium(III)

Zirconium(IV)

Hafnium(IV)

Metal cations

Tetravalent actinides

Structural studies

Résumé

Pas de résumé en français

The goal of this research was the synthesis and spectroscopic, structural andphysical-chemical characterization of cyclic 6- and 7-membered hydroxamicacids, a tetrahydroxamic calix[4]arene-based tetrapodal receptor, and their metalcomplexes with trivalent and tetravalent metal cations. They were characterizedby several techniques such as 1H and 13C NMR, IR, and mass spectroscopies,single crystal X-ray analysis, and potentiometry. Cyclic hydroxamic acids arefound in a few mix siderophores but their coordination properties were stillunknown. The structural features of metal complexes formed with Fe(III),Ga(III), Ce(IV), Zr(IV), Hf(IV), U(IV) and U(VI) have been investigated both inthe solid state and in solution. The synthesis and complexation studies of anoriginal calix[4]arene-based tetrapodal receptor is described. Reactionparameters for all key steps in the synthetic route have been optimized. Thesingle X-ray crystal analysis of benzyl-protected receptor was obtained.Complexation studies with zirconium(IV) and hafnium(IV) evidenced theformation of two metal two ligand complexes rather than 1:1 species, whichwere shown to interact in solution with a third alkali cation