[SiR3]. Dans ce cas le ligand silylium doit tre considr comme un ligand Z en appliquant le formalisme de Green, ce qui suggre un tat d'oxidation formel de +Ill pour l'atome d'iridium. Cette thse a contribu une meilleure comprhension de la chimie du silylium applique la chimie organomtallique, et a abouti l'mergence d'un nouveau champ de recherche qui pourra permettre l'laboration de nouveaux prcatalyseurs multicomptents. A new family of highly active iridacyclic lr(lll) precatalysts has been discovered. Notably, these ionic iridacycles are very stable so that their handling under air whether in solution or as solid powder is possible. The relative simplicity of their molecular structures allows their preparation on gram scale through a very simple and convenient synthetic protocol. We identified important iridium-silane intermediates involved in the catalysis of various reactions, e.g. the 0-silylation of alcohols, the hydrosilylation of CO and CN functions, and the activation of the C(sp3)-F bond of fluorocarbons. Experimental and theoretical studies of these intermediates point towards a Lewis donor-acceptor structural formulation of the type [lr(lll)H] >[SiR3]. These results constitute a significant contribution to the design of future multicompetent precatalysts, and provide an original insight to the bonding within the Si-lr-H motif by considering the silylium ion [SiR3]+ as a Z-type ligand rather than a "traditional" X ligand.Advisors/Committee Members: Djukic, Jean-Pierre (thesis director).'>

Abstracts

Study and applications of the H-Si bond activation of silanes by iridacycles : a contribution to the design of multicompetent catalysts : Etude et applications de la raction d'activation des silanes par les iridacycles : une contribution l'laboration de catalyseurs multicomptents

by Mustapha Hamdaoui




Institution: Universit de Strasbourg
Department:
Year: 2017
Keywords: Iridacycles ioniques; Catalyse homogne; O-silylation; Hydrosilylation; Activation CF; Intermdiaires donneur-accepteur; [Ir(III)H][SiR3]; Ion silylium; Ligand Z; Ionic iridacycles; Homogeneous catalysis; O-silylation; Hydrosilylation; CF bond activation; Donor-acceptor intermediates; [Ir(III)H][SiR3]; Silylium ion; Z ligand; 541.3
Posted: 02/01/2018
Record ID: 2162783
Full text PDF: http://www.theses.fr/2017STRAF007


Abstract

Une nouvelle famille de prcatalyseurs base d'lr(lll) a t dcouverte. La facilit de leur prparation, leur remarquable stabilit, et surtout leur excellente efficacit catalytique dans plusieurs ractions, c.--d. la 0-silylation d'alcools, l'hydrosilylation de fonctions CO et CN et l'activation de la liaison C-F, constituent un ensemble de proprits que d'autres prcatalyseurs organomtalliques similaires connus ce jour ne possdent pas. Le fait le plus significatif est la mise en vidence exprimentale et thorique que les espces catalytiques impliques fonctionnement comme une paire de Lewis du type donneur-accepteur [lr(lll)H] >[SiR3]. Dans ce cas le ligand silylium doit tre considr comme un ligand Z en appliquant le formalisme de Green, ce qui suggre un tat d'oxidation formel de +Ill pour l'atome d'iridium. Cette thse a contribu une meilleure comprhension de la chimie du silylium applique la chimie organomtallique, et a abouti l'mergence d'un nouveau champ de recherche qui pourra permettre l'laboration de nouveaux prcatalyseurs multicomptents. A new family of highly active iridacyclic lr(lll) precatalysts has been discovered. Notably, these ionic iridacycles are very stable so that their handling under air whether in solution or as solid powder is possible. The relative simplicity of their molecular structures allows their preparation on gram scale through a very simple and convenient synthetic protocol. We identified important iridium-silane intermediates involved in the catalysis of various reactions, e.g. the 0-silylation of alcohols, the hydrosilylation of CO and CN functions, and the activation of the C(sp3)-F bond of fluorocarbons. Experimental and theoretical studies of these intermediates point towards a Lewis donor-acceptor structural formulation of the type [lr(lll)H] >[SiR3]. These results constitute a significant contribution to the design of future multicompetent precatalysts, and provide an original insight to the bonding within the Si-lr-H motif by considering the silylium ion [SiR3]+ as a Z-type ligand rather than a "traditional" X ligand.Advisors/Committee Members: Djukic, Jean-Pierre (thesis director).