LCC - Centre de Ressources Documentaires
Détail de l'auteur
Auteur Rinaldo Poli |
Documents disponibles écrits par cet auteur (20)
Faire une suggestion Affiner la rechercheUtilisation de ligands bifonctionnels chiraux pour la catalyse asymétrique impliquant des complexes d'hydrures / Raluca Malacea
Titre : Utilisation de ligands bifonctionnels chiraux pour la catalyse asymétrique impliquant des complexes d'hydrures Titre original : Use of chiral bifonctional ligands for asymmetric catalysis involing hydrides Type de document : texte imprimé Auteurs : Raluca Malacea, Auteur ; Rinaldo Poli, Directeur de thèse Langues : Français (fre) Tags : HYDROGENATION COMPOSES INTERMÉTALLIQUE HYDRURE CATALYSE ASYMÉTRIQUE LIGANDS (BIOCHIMIE) AMINO-PHOSPHINE FERROCENE PHOSPHINES THIOÉTHER SULFOXYDES PARA-HYDROGENE
HYDROGENATION INTERMETALLIC COMPOUNDS HYDRIDE ASYMMETRIC CATALYSIS LIGANDS (BIOCHEMISTRY) THIOETHER SULFOXIDES PARA-HYDROGENRésumé : "Après une introduction bibliographique sur les ligands bifonctionnels P,N et P,S utilisés en catalyse asymétrique (Chapitre I), le chapitre II décrit la synthèse de nouveaux composés P,P-diaminoalkyl-phosphine et P,P,P-triamino-phosphine dérivés de diamines chirales et leur utilisation dans l'hydroformylation du styrène. Dans le chapitre III, nous avons étudié la chimie de coordination de ligands phosphine-thioéther ferrocéniques chiraux avec le platine, le palladium, l'iridium, le rhodium et le ruthénium pour donner une grande variété des complexes. La chiralité planaire du ferrocène contrôle la configuration du soufre asymétrique, crée par complexation. Les complexes d'iridium ont donné de très bonnes activités et énantiosélectivités ( e. E. Jusqu'à 99%) dans l'hydrogénation asymétrique de cétones."
"After a bibliographic introduction on bifonctional P,N and P,S ligands used in asymmetric catalysis (Chapter I), in the chapter II is described the synthesis of new compounds P,P-diaminoalkyl-phosphine and P,P,P-triamino-phosphine from chiral damines and their application in styrene hydroformylation. In the third chapter, we studied the coordination chemistry of chiral phosphine-thioether ferrocenic ligands with platinum, palladium, iridium, rhodium and ruthenium and we obtained a great variety of complexes. The configuration of the sulphur atom, which became asymmetric after coordination, is totally controlled by the planar chirality of ferrocene. Iridium complexes gave high activity and excellent enantioselectivity (e. E. Up to 99%) in the asymmetric hydrogenation of ketones."Document : Thèse de Doctorat Etablissement_delivrance : Université Toulouse 3 Date_soutenance : 02/06/2006 Domaine : Chimie Organométallique et Coordination En ligne : https://www.theses.fr/2006TOU30054 Utilisation de ligands bifonctionnels chiraux pour la catalyse asymétrique impliquant des complexes d'hydrures = Use of chiral bifonctional ligands for asymmetric catalysis involing hydrides [texte imprimé] / Raluca Malacea, Auteur ; Rinaldo Poli, Directeur de thèse . - [s.d.].
Langues : Français (fre)
Tags : HYDROGENATION COMPOSES INTERMÉTALLIQUE HYDRURE CATALYSE ASYMÉTRIQUE LIGANDS (BIOCHIMIE) AMINO-PHOSPHINE FERROCENE PHOSPHINES THIOÉTHER SULFOXYDES PARA-HYDROGENE
HYDROGENATION INTERMETALLIC COMPOUNDS HYDRIDE ASYMMETRIC CATALYSIS LIGANDS (BIOCHEMISTRY) THIOETHER SULFOXIDES PARA-HYDROGENRésumé : "Après une introduction bibliographique sur les ligands bifonctionnels P,N et P,S utilisés en catalyse asymétrique (Chapitre I), le chapitre II décrit la synthèse de nouveaux composés P,P-diaminoalkyl-phosphine et P,P,P-triamino-phosphine dérivés de diamines chirales et leur utilisation dans l'hydroformylation du styrène. Dans le chapitre III, nous avons étudié la chimie de coordination de ligands phosphine-thioéther ferrocéniques chiraux avec le platine, le palladium, l'iridium, le rhodium et le ruthénium pour donner une grande variété des complexes. La chiralité planaire du ferrocène contrôle la configuration du soufre asymétrique, crée par complexation. Les complexes d'iridium ont donné de très bonnes activités et énantiosélectivités ( e. E. Jusqu'à 99%) dans l'hydrogénation asymétrique de cétones."
"After a bibliographic introduction on bifonctional P,N and P,S ligands used in asymmetric catalysis (Chapter I), in the chapter II is described the synthesis of new compounds P,P-diaminoalkyl-phosphine and P,P,P-triamino-phosphine from chiral damines and their application in styrene hydroformylation. In the third chapter, we studied the coordination chemistry of chiral phosphine-thioether ferrocenic ligands with platinum, palladium, iridium, rhodium and ruthenium and we obtained a great variety of complexes. The configuration of the sulphur atom, which became asymmetric after coordination, is totally controlled by the planar chirality of ferrocene. Iridium complexes gave high activity and excellent enantioselectivity (e. E. Up to 99%) in the asymmetric hydrogenation of ketones."Document : Thèse de Doctorat Etablissement_delivrance : Université Toulouse 3 Date_soutenance : 02/06/2006 Domaine : Chimie Organométallique et Coordination En ligne : https://www.theses.fr/2006TOU30054
Titre : Utilisation de complexes de molybdène pour l'étude de mécanismes de contrôle en polymérisation radicalaire Titre original : Utilization of molybdenum complexes for the study of control mechanisms in radical polymerization Type de document : texte imprimé Auteurs : Sébastien Maria, Auteur ; Rinaldo Poli, Directeur de thèse Langues : Français (fre) Tags : LIQUIDES IONIQUES POLYMÉRISATION CATALYSEURS AU MOLYBDÈNE MOLYBDÈNE -COMPOSÉ
IONIC LIQUIDS POLYMERIZATION MOLYBDENUM CATALYSTS MOLYBDENUM COMPOUNDRésumé : "Les catalyseurs MoX3(PMe3)3 (X = Cl, Br, I) pour la polymérisation radicalaire par transfert d'atome (ATRP) du styrène, ont été étudiés par voltamétrie cyclique, par oxydation avec des dihalogènes (synthèse de MoBr4(PMe3)3 et [PIMe3][MoI4(PMe3)2]) et à l'aide de calculs théoriques, permettant de montrer que le piège à radicaux en ATRP n'a pas besoin d'être thermodynamiquement stable. L'action de ces composés en ATRP dans un solvant ionique et en polymérisation en présence de radicaux stables (SFRP) a aussi fait l'objet d'investigations. MoI2O(PMe3)3 a été synthétisé et caractérisé. Ce composé et MoCl2O(PMe3)3 sont les complexes de coordination de molybdène les plus actifs pour l'ATRP du styrène et les premiers au degré d'oxydation IV."
"The MoX3(PMe3)3 (X = Cl, Br, I) catalysts for the Atom Transfer Radical Polymerization of styrene have been studied by cyclic voltammetry, by oxidation with dihalogens (synthesis of MoBr4(PMe3)3 and [PIMe3][MoI4(PMe3)2]) and with the help of theoretical calculations, allowing us to show that the ATRP radical trap does not need to be thermodynamically stable. The behaviour of these compounds in ATRP conditions, using ionics liquids, and in Stable Free Radical Polymerization (SFRP) conditions, has also been investigated. MoI2O(PMe3)3 has been synthesized and characterized. This compound, together with MoCl2O(PMe3)3, is the most active molybdenum coordination complex for styrene ATRP, and the first one in the oxidation state IV."Document : Thèse de Doctorat Etablissement_delivrance : Université Dijon Date_soutenance : 17/03/2006 Domaine : Chimie - Physique En ligne : https://www.theses.fr/2006DIJOS007 Utilisation de complexes de molybdène pour l'étude de mécanismes de contrôle en polymérisation radicalaire = Utilization of molybdenum complexes for the study of control mechanisms in radical polymerization [texte imprimé] / Sébastien Maria, Auteur ; Rinaldo Poli, Directeur de thèse . - [s.d.].
Langues : Français (fre)
Tags : LIQUIDES IONIQUES POLYMÉRISATION CATALYSEURS AU MOLYBDÈNE MOLYBDÈNE -COMPOSÉ
IONIC LIQUIDS POLYMERIZATION MOLYBDENUM CATALYSTS MOLYBDENUM COMPOUNDRésumé : "Les catalyseurs MoX3(PMe3)3 (X = Cl, Br, I) pour la polymérisation radicalaire par transfert d'atome (ATRP) du styrène, ont été étudiés par voltamétrie cyclique, par oxydation avec des dihalogènes (synthèse de MoBr4(PMe3)3 et [PIMe3][MoI4(PMe3)2]) et à l'aide de calculs théoriques, permettant de montrer que le piège à radicaux en ATRP n'a pas besoin d'être thermodynamiquement stable. L'action de ces composés en ATRP dans un solvant ionique et en polymérisation en présence de radicaux stables (SFRP) a aussi fait l'objet d'investigations. MoI2O(PMe3)3 a été synthétisé et caractérisé. Ce composé et MoCl2O(PMe3)3 sont les complexes de coordination de molybdène les plus actifs pour l'ATRP du styrène et les premiers au degré d'oxydation IV."
"The MoX3(PMe3)3 (X = Cl, Br, I) catalysts for the Atom Transfer Radical Polymerization of styrene have been studied by cyclic voltammetry, by oxidation with dihalogens (synthesis of MoBr4(PMe3)3 and [PIMe3][MoI4(PMe3)2]) and with the help of theoretical calculations, allowing us to show that the ATRP radical trap does not need to be thermodynamically stable. The behaviour of these compounds in ATRP conditions, using ionics liquids, and in Stable Free Radical Polymerization (SFRP) conditions, has also been investigated. MoI2O(PMe3)3 has been synthesized and characterized. This compound, together with MoCl2O(PMe3)3, is the most active molybdenum coordination complex for styrene ATRP, and the first one in the oxidation state IV."Document : Thèse de Doctorat Etablissement_delivrance : Université Dijon Date_soutenance : 17/03/2006 Domaine : Chimie - Physique En ligne : https://www.theses.fr/2006DIJOS007
Titre : Arene ruthenium iminophosphonamide complexes : synthesis, reactivity and application in transfer hydrogenation of ketones Type de document : texte imprimé Auteurs : Iana Sinopalnikova, Auteur ; Rinaldo Poli, Directeur de thèse ; Alexander Kalsin, Directeur de thèse Langues : Anglais (eng) Tags : RUTHENIUM COMPLEXES ZWITTERIOINIC LIGANDS CHLORIDE DISSOCIATION CARBONYLATION TRANSFER HYDROGENATION ACTIVATION MECHANISM Résumé : "Novel half-sandwich 18? and 16? arene ruthenium iminophosphonamide (NPN) complexes [(?6-Arene)RuCl{R2P(NR')2}] (3a-c,e,f), [(?6-C6Me6)RuCl{Ph2P(N-Me)(N-p-Tol)}] (3d) and [(?6-arene)Ru{R2P(NR')2}]+(X-) (4a-c,f) (a, R = Ph, R' = p-Tol; b, R = Et, R' = p-Tol; c, R = Ph, R' = Me; e, R = Ph, R' = p-C6H4COOEt; f, R = Ph, R' = p-Tol. X = BF4, PF6. Arene = C6Me6, p-Cymene) were synthesized and fully characterized. The thermodynamics of chloride dissociation from the 18? NPN complexes has been assessed in both polar and apolar solvents, using variable-temperature UV-visible, NMR and 2D EXSY 1H NMR methods, highlighting the NPN ligand influence on the equilibrium parameters. The dissociation enthalpy ?Hd decreases upon increasing the electron-donating ability of the N-,P- substituents (3e > 3a,f > 3b > 3d > 3c) and the solvent polarity, resulting in the exothermic spontaneous dissociation of 3c in polar solvents. The coordination of neutral ligands (MeCN, pyridine, CO) to the corresponding 16? complexes 4a,c,f is reversible; the stability of the adducts depends on the ?-accepting ability of ligand. Carbonylation of 4a and 4f results rare examples of cationic arene ruthenium carbonyl complexes (5a, 5f), while the monocarbonyl adduct derived from 4c reacts further with a second CO molecule, rapidly converting to the carbonyl-carbamoyl complex 5c', where one CO molecule is inserted into the Ru-N bond. The new carbonyl complexes 5a,f and 5c' were isolated and structurally characterized. For the first time, it has been shown that ruthenium NPN complexes are active catalysts for the transfer hydrogenation of ketones. The catalytic activity increases with the introduction of the p-cymene arene ligand and more electron-donating N substituents. The complexes containing NPN ligands with N-Aryl substitution are activated by a strong base. Model reactions and kinetic studies, backed up by DFT calculations, have established that the key intermediate is a hydride complex. The complexes with N-Me substituted are activated without base, for them we propose cationic complex to be an active intermediate." Document : Thèse de Doctorat Etablissement_delivrance : Université deToulouse 3 Date_soutenance : 21/06/2019 Ecole_doctorale : Sciences de la Matière (SdM) (Toulouse) Domaine : Chimie organométallique et de coordination En ligne : https://theses.hal.science/tel-02880098 Arene ruthenium iminophosphonamide complexes : synthesis, reactivity and application in transfer hydrogenation of ketones [texte imprimé] / Iana Sinopalnikova, Auteur ; Rinaldo Poli, Directeur de thèse ; Alexander Kalsin, Directeur de thèse . - [s.d.].
Langues : Anglais (eng)
Tags : RUTHENIUM COMPLEXES ZWITTERIOINIC LIGANDS CHLORIDE DISSOCIATION CARBONYLATION TRANSFER HYDROGENATION ACTIVATION MECHANISM Résumé : "Novel half-sandwich 18? and 16? arene ruthenium iminophosphonamide (NPN) complexes [(?6-Arene)RuCl{R2P(NR')2}] (3a-c,e,f), [(?6-C6Me6)RuCl{Ph2P(N-Me)(N-p-Tol)}] (3d) and [(?6-arene)Ru{R2P(NR')2}]+(X-) (4a-c,f) (a, R = Ph, R' = p-Tol; b, R = Et, R' = p-Tol; c, R = Ph, R' = Me; e, R = Ph, R' = p-C6H4COOEt; f, R = Ph, R' = p-Tol. X = BF4, PF6. Arene = C6Me6, p-Cymene) were synthesized and fully characterized. The thermodynamics of chloride dissociation from the 18? NPN complexes has been assessed in both polar and apolar solvents, using variable-temperature UV-visible, NMR and 2D EXSY 1H NMR methods, highlighting the NPN ligand influence on the equilibrium parameters. The dissociation enthalpy ?Hd decreases upon increasing the electron-donating ability of the N-,P- substituents (3e > 3a,f > 3b > 3d > 3c) and the solvent polarity, resulting in the exothermic spontaneous dissociation of 3c in polar solvents. The coordination of neutral ligands (MeCN, pyridine, CO) to the corresponding 16? complexes 4a,c,f is reversible; the stability of the adducts depends on the ?-accepting ability of ligand. Carbonylation of 4a and 4f results rare examples of cationic arene ruthenium carbonyl complexes (5a, 5f), while the monocarbonyl adduct derived from 4c reacts further with a second CO molecule, rapidly converting to the carbonyl-carbamoyl complex 5c', where one CO molecule is inserted into the Ru-N bond. The new carbonyl complexes 5a,f and 5c' were isolated and structurally characterized. For the first time, it has been shown that ruthenium NPN complexes are active catalysts for the transfer hydrogenation of ketones. The catalytic activity increases with the introduction of the p-cymene arene ligand and more electron-donating N substituents. The complexes containing NPN ligands with N-Aryl substitution are activated by a strong base. Model reactions and kinetic studies, backed up by DFT calculations, have established that the key intermediate is a hydride complex. The complexes with N-Me substituted are activated without base, for them we propose cationic complex to be an active intermediate." Document : Thèse de Doctorat Etablissement_delivrance : Université deToulouse 3 Date_soutenance : 21/06/2019 Ecole_doctorale : Sciences de la Matière (SdM) (Toulouse) Domaine : Chimie organométallique et de coordination En ligne : https://theses.hal.science/tel-02880098
Titre : From homogeneous to heterogeneous catalysis for solvent-free olefin epoxidation using molybdenum pre-catalysts Type de document : texte imprimé Auteurs : Weili Wang, Auteur ; Rinaldo Poli, Directeur de thèse ; Dominique Agustin, Directeur de thèse Langues : Français (fre) Tags : HOMOGENEOUS CATALYSIS HETEROGENEOUS CATALYSIS EPOXIDATION WITHOUT ORGANIC SOLVENT MOLYBDENUM GREEN CHEMISTRY GRAFTING ON SUPPORT LIMONENE CYCLOOCTENE Résumé : "The work of this PhD thesis deals with the study of molybdenum complexes of general formula
[MoO2L]n (L being a tridentate Schiff base ligand with an ONO or ONS coordination sphere around the
molybdenum) as catalysts for the organic solvent-free epoxidation of olefins. Within the spirit of Green
Chemistry, the work has focused on four of the twelve Green Chemistry principles: the use of catalysis
rather than stoichiometric transformations, the use of organic solvent-free procedures rather than
operating in solution of organic solvents, the use of renewable substrates and the grafting of catalysts for
their recovery.
The first part of the manuscript presents a concise state of the art on the chemistry of molybdenum
complexes with ligands similar to those used within the thesis. Specific aspects such as the effect of
ligand substituents and the different activities – mainly catalytic – observed in organic media are
reviewed. A section of this chapter is dedicated to the different strategies employed for the grafting of
molybdenum complexes to solid supports as well as to the use of the resulting supported complexes in
heterogenized homogeneous catalysis.
The next chapter details the synthesis and characterization of all the molecular complexes used as
catalysts. This chapter shows the different substitutions operated on the ligands, i.e. changing the ONO
coordination sphere to ONS and adding different substituents on the ligands, i.e. OH free functions or
additional donor (diethylamino) and/or withdrawing (nitro) substituents at different positions on the
tridentate ligand in order to modify the catalytic activity. Six of the synthesized complexes could be
characterized by X-ray crystallography.
The third chapter reports the results obtained for the catalyzed organic solvent-free epoxidation of
cyclooctene as a model substrate using all the molybdenum complexes presented in the previous chapter.
It is shown that the nature of the coordination sphere around the molybdenum (ONO vs ONS) is in favour
of the latter in terms of catalytic activity towards the formation of the desired epoxide. The catalyzed
reactions with complexes containing an OH substituent at different positions on the aromatic ring have
shown more significant effects in the case of the ONO coordination sphere than in the corresponding
ONS case. The epoxidation performed in the presence of a dimethylamino and/or a nitro substituent on
the ONO ligand revealed that the catalytic activity is enhanced by the electron withdrawing group.
The catalytic investigations were pursued by the epoxidation of cyclohexene and of one natural
substrate, limonene. This study has shown that limonene oxides and/or limonene diols are generated,
depending on the nature of the catalyst. The ONS complexes are very reactive and quickly lead to the
limonene diols. The effect of different parameters has been studied with particular attention to the
reaction temperature.
Finally, one stable molybdenum complex with an ONO coordination sphere has been grafted onto a
commercial Merrifield resin. Different grafting strategies are presented. The isolated objects have been
tested as catalysts under organic solvent-free conditions for the epoxidation of cyclooctene. The catalytic
results are promising in terms of activity and the recovery/recycling tests have shown that the catalysts
could be used three times without significant decrease of conversion and selectivity, but some metal
leaching was observed."
Document : Thèse de Doctorat Etablissement_delivrance : Université Toulouse 3 Date_soutenance : 17/09/2015 Ecole_doctorale : Sciences de la matière (SdM) Domaine : Chimie organométallique de coordination En ligne : http://thesesups.ups-tlse.fr/2917/ From homogeneous to heterogeneous catalysis for solvent-free olefin epoxidation using molybdenum pre-catalysts [texte imprimé] / Weili Wang, Auteur ; Rinaldo Poli, Directeur de thèse ; Dominique Agustin, Directeur de thèse . - [s.d.].
Langues : Français (fre)
Tags : HOMOGENEOUS CATALYSIS HETEROGENEOUS CATALYSIS EPOXIDATION WITHOUT ORGANIC SOLVENT MOLYBDENUM GREEN CHEMISTRY GRAFTING ON SUPPORT LIMONENE CYCLOOCTENE Résumé : "The work of this PhD thesis deals with the study of molybdenum complexes of general formula
[MoO2L]n (L being a tridentate Schiff base ligand with an ONO or ONS coordination sphere around the
molybdenum) as catalysts for the organic solvent-free epoxidation of olefins. Within the spirit of Green
Chemistry, the work has focused on four of the twelve Green Chemistry principles: the use of catalysis
rather than stoichiometric transformations, the use of organic solvent-free procedures rather than
operating in solution of organic solvents, the use of renewable substrates and the grafting of catalysts for
their recovery.
The first part of the manuscript presents a concise state of the art on the chemistry of molybdenum
complexes with ligands similar to those used within the thesis. Specific aspects such as the effect of
ligand substituents and the different activities – mainly catalytic – observed in organic media are
reviewed. A section of this chapter is dedicated to the different strategies employed for the grafting of
molybdenum complexes to solid supports as well as to the use of the resulting supported complexes in
heterogenized homogeneous catalysis.
The next chapter details the synthesis and characterization of all the molecular complexes used as
catalysts. This chapter shows the different substitutions operated on the ligands, i.e. changing the ONO
coordination sphere to ONS and adding different substituents on the ligands, i.e. OH free functions or
additional donor (diethylamino) and/or withdrawing (nitro) substituents at different positions on the
tridentate ligand in order to modify the catalytic activity. Six of the synthesized complexes could be
characterized by X-ray crystallography.
The third chapter reports the results obtained for the catalyzed organic solvent-free epoxidation of
cyclooctene as a model substrate using all the molybdenum complexes presented in the previous chapter.
It is shown that the nature of the coordination sphere around the molybdenum (ONO vs ONS) is in favour
of the latter in terms of catalytic activity towards the formation of the desired epoxide. The catalyzed
reactions with complexes containing an OH substituent at different positions on the aromatic ring have
shown more significant effects in the case of the ONO coordination sphere than in the corresponding
ONS case. The epoxidation performed in the presence of a dimethylamino and/or a nitro substituent on
the ONO ligand revealed that the catalytic activity is enhanced by the electron withdrawing group.
The catalytic investigations were pursued by the epoxidation of cyclohexene and of one natural
substrate, limonene. This study has shown that limonene oxides and/or limonene diols are generated,
depending on the nature of the catalyst. The ONS complexes are very reactive and quickly lead to the
limonene diols. The effect of different parameters has been studied with particular attention to the
reaction temperature.
Finally, one stable molybdenum complex with an ONO coordination sphere has been grafted onto a
commercial Merrifield resin. Different grafting strategies are presented. The isolated objects have been
tested as catalysts under organic solvent-free conditions for the epoxidation of cyclooctene. The catalytic
results are promising in terms of activity and the recovery/recycling tests have shown that the catalysts
could be used three times without significant decrease of conversion and selectivity, but some metal
leaching was observed."
Document : Thèse de Doctorat Etablissement_delivrance : Université Toulouse 3 Date_soutenance : 17/09/2015 Ecole_doctorale : Sciences de la matière (SdM) Domaine : Chimie organométallique de coordination En ligne : http://thesesups.ups-tlse.fr/2917/
Titre : New approach to aqueous biphasic catalysis through catalyst confinement in nanoscopic core-shell polymers Type de document : texte imprimé Auteurs : Si Chen, Auteur ; Rinaldo Poli, Directeur de thèse ; Manoury, Eric, Directeur de thèse Langues : Anglais (eng) Tags : CORE-SHELL POLYMERS CATALYTIC NANOREACTORS MACROMOLECULAR RAFT - BIPHASIC CATALYSIS EMULSION POLYMERIZATION HYDROFORMYLATION PISA Résumé : "The catalytic processes are at the heart of chemical industry. Modern chemical industry, under pressure of
stricter regulations and societal concern, is faced with the need to improve efficiency and cleaner production
processes and catalysis is one the major keys to green chemical technology. Catalysts recovery is necessary
from an economic and environmental point of view when it makes use of expensive and / or toxic metals. The
aim of this thesis is based on an innovative approach related to micellar catalyst but in which the catalyst is
covalent linked to the hydrophobic core of well-defined unimolecular, core-cross-linked micelles. The
synthetic protocol is based on a convergent method via RAFT-mediated one-pot aqueous emulsion
polymerization. The efficiency of these unimolecular micelles as catalytic nanoreactors has been shown using
the industrially relevant hydroformylation of 1-octene, in order to provide a proof of principle, as a test
reaction yielding turnover frequencies and l/b ratio comparable to those of related homogeneous systems.
However, the catalyst phase could be easily separated from the organic product phase and recycled. A
remarkable protecting effect of the active catalyst by the polymer scaffold has also been demonstrated. The
absence of the coagulation at the end of reaction is evidence that these new objects function as micelles while
eliminating the disadvantages of micellar catalysis such as the formation of stable emulsion."Document : Thèse de Doctorat Etablissement_delivrance : Université Toulouse 3 Date_soutenance : 28/09/2015 Ecole_doctorale : Sciences de la matière (SdM) Domaine : Chimie Moléculaire, industrielle, polymères En ligne : http://thesesups.ups-tlse.fr/2906/ New approach to aqueous biphasic catalysis through catalyst confinement in nanoscopic core-shell polymers [texte imprimé] / Si Chen, Auteur ; Rinaldo Poli, Directeur de thèse ; Manoury, Eric, Directeur de thèse . - [s.d.].
Langues : Anglais (eng)
Tags : CORE-SHELL POLYMERS CATALYTIC NANOREACTORS MACROMOLECULAR RAFT - BIPHASIC CATALYSIS EMULSION POLYMERIZATION HYDROFORMYLATION PISA Résumé : "The catalytic processes are at the heart of chemical industry. Modern chemical industry, under pressure of
stricter regulations and societal concern, is faced with the need to improve efficiency and cleaner production
processes and catalysis is one the major keys to green chemical technology. Catalysts recovery is necessary
from an economic and environmental point of view when it makes use of expensive and / or toxic metals. The
aim of this thesis is based on an innovative approach related to micellar catalyst but in which the catalyst is
covalent linked to the hydrophobic core of well-defined unimolecular, core-cross-linked micelles. The
synthetic protocol is based on a convergent method via RAFT-mediated one-pot aqueous emulsion
polymerization. The efficiency of these unimolecular micelles as catalytic nanoreactors has been shown using
the industrially relevant hydroformylation of 1-octene, in order to provide a proof of principle, as a test
reaction yielding turnover frequencies and l/b ratio comparable to those of related homogeneous systems.
However, the catalyst phase could be easily separated from the organic product phase and recycled. A
remarkable protecting effect of the active catalyst by the polymer scaffold has also been demonstrated. The
absence of the coagulation at the end of reaction is evidence that these new objects function as micelles while
eliminating the disadvantages of micellar catalysis such as the formation of stable emulsion."Document : Thèse de Doctorat Etablissement_delivrance : Université Toulouse 3 Date_soutenance : 28/09/2015 Ecole_doctorale : Sciences de la matière (SdM) Domaine : Chimie Moléculaire, industrielle, polymères En ligne : http://thesesups.ups-tlse.fr/2906/
Permalink
Permalink
PermalinkPermalink
Permalink
Permalink
Permalink
Permalink
PermalinkPermalink
Permalink
Permalink
Permalink
Permalink
Permalink
