| Titre : |
New chiral phosphine based ligands for asymmetric hydrogenation |
| Type de document : |
texte imprimé |
| Auteurs : |
Wei, Muh-Mei, Auteur ; Manoury, Eric, Directeur de thèse ; Eric Deydier, Directeur de thèse |
| Année de publication : |
2013 |
| Langues : |
Anglais (eng) |
| Tags : |
PHOSPHINE LIGANDS FERROCENE LIGANDS CHIRAL LIGANDS COORDINATION CHEMISTRY DFT CALCULATION ASYMMETRIC HYDROGENATION NANOPARTICLES ARENE HYDROGENATION |
| Résumé : |
"Asymmetric hydrogenation has advanced the field of asymmetric catalytic technology. Chiral phosphine based ligands have played a significant role for asymmetric hydrogenation. The first part of the thesis is devoted to the synthesis and characterization of new P,N ferrocenyl ligands {1,2-(TosNRCH2)(PPh2)C5H3}FeCp (R = H, Me) and their coordination chemistry with [Ru(p-cymene)Cl2]2, [RhCp*Cl2]2, [IrCp*Cl2]2, [Rh(COD)Cl]2 and [Ir(COD)Cl]2. Intra and inter molecular N-H···Cl bonds were investigated by variable temperature NMR and DFT calculations. Addition of triethylamine to the complexes with R = H allows removing the tosylamide acidic hydrogen atom giving rise to a ferrocenyl amidophosphine ligand coordinated in a bidendate fashion (ê2:P,N). Several complexes were assessed as precatalysts in the hydrogenation and transfer hydrogenation of acetophenone. Heterogeneous hydrogenation catalysis of the arene was observed in the presence of the RhI complex. The TEM and high resolution TEM showed the formation of metallic nanoparticles. In the second part, new P,S ferrocene-based {1,2-(BrC6H4SCH2)(PPh2)C5H3}FeCp ligands have been successfully synthesized and characterized in view of the catalysts anchored on mesoporous materials. In the final part, new complexes of a C2-symmetric bistriazolyl diphosphine coordinated to [Ir(COD)Cl]2, [PtCl2(PhCN)2] and [PdBr2(CH3CN)2] have been synthesized and characterized. The coordination chemistry with [Ir(COD)Cl]2 has been studied as a function of the P/Ir ratio. Hydrogenation and transfer hydrogenation processes catalyzed by these Ir complexes have been investigated, with excellent activities found for the hydrogenation of imines." |
| Document : |
Thèse de Doctorat |
| Etablissement_delivrance : |
Université de Toulouse 3 |
| Date_soutenance : |
17/12/2013 |
| Ecole_doctorale : |
Sciences de la matière (SdM) |
| Domaine : |
Chimie organométallique de coordination |
| En ligne : |
http://thesesups.ups-tlse.fr/2240/ |
New chiral phosphine based ligands for asymmetric hydrogenation [texte imprimé] / Wei, Muh-Mei, Auteur ; Manoury, Eric, Directeur de thèse ; Eric Deydier, Directeur de thèse . - 2013. Langues : Anglais ( eng)
| Tags : |
PHOSPHINE LIGANDS FERROCENE LIGANDS CHIRAL LIGANDS COORDINATION CHEMISTRY DFT CALCULATION ASYMMETRIC HYDROGENATION NANOPARTICLES ARENE HYDROGENATION |
| Résumé : |
"Asymmetric hydrogenation has advanced the field of asymmetric catalytic technology. Chiral phosphine based ligands have played a significant role for asymmetric hydrogenation. The first part of the thesis is devoted to the synthesis and characterization of new P,N ferrocenyl ligands {1,2-(TosNRCH2)(PPh2)C5H3}FeCp (R = H, Me) and their coordination chemistry with [Ru(p-cymene)Cl2]2, [RhCp*Cl2]2, [IrCp*Cl2]2, [Rh(COD)Cl]2 and [Ir(COD)Cl]2. Intra and inter molecular N-H···Cl bonds were investigated by variable temperature NMR and DFT calculations. Addition of triethylamine to the complexes with R = H allows removing the tosylamide acidic hydrogen atom giving rise to a ferrocenyl amidophosphine ligand coordinated in a bidendate fashion (ê2:P,N). Several complexes were assessed as precatalysts in the hydrogenation and transfer hydrogenation of acetophenone. Heterogeneous hydrogenation catalysis of the arene was observed in the presence of the RhI complex. The TEM and high resolution TEM showed the formation of metallic nanoparticles. In the second part, new P,S ferrocene-based {1,2-(BrC6H4SCH2)(PPh2)C5H3}FeCp ligands have been successfully synthesized and characterized in view of the catalysts anchored on mesoporous materials. In the final part, new complexes of a C2-symmetric bistriazolyl diphosphine coordinated to [Ir(COD)Cl]2, [PtCl2(PhCN)2] and [PdBr2(CH3CN)2] have been synthesized and characterized. The coordination chemistry with [Ir(COD)Cl]2 has been studied as a function of the P/Ir ratio. Hydrogenation and transfer hydrogenation processes catalyzed by these Ir complexes have been investigated, with excellent activities found for the hydrogenation of imines." |
| Document : |
Thèse de Doctorat |
| Etablissement_delivrance : |
Université de Toulouse 3 |
| Date_soutenance : |
17/12/2013 |
| Ecole_doctorale : |
Sciences de la matière (SdM) |
| Domaine : |
Chimie organométallique de coordination |
| En ligne : |
http://thesesups.ups-tlse.fr/2240/ |
|  |
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