19 recherche sur le tag 'ruthenium'   

Ruthenium complexes / Holder, Alvin A.

Public ISBD Titre : Ruthenium complexes : Photomedical and biomedical applications Type de document : texte imprimé Auteurs : Holder, Alvin A., Auteur ; Lilge, Lothar, Auteur ; Browne, Wesley R., Auteur ; Lawrence, Mark A. W., Auteur ; Bullock Jr., Jimmie L., Auteur Editeur : New York : Wiley Année de publication : 2018 Importance : xx, 324 p. ISBN/ISSN/EAN : 978-3-527-33957-0 Langues : Anglais (eng) Catégories : Chimie de coordination, Chimie organométallique, Métaux de transition Tags : RUTHENIUM Index. décimale : B-D Résumé : Edited by a team of highly respected researchers combining their expertise in chemistry, physics, and medicine, this book focuses on the use of rutheniumcontaining complexes in artificial photosynthesis and medicine. Following a brief introduction to the basic coordination chemistry of ruthenium complexes and their synthesis in section one, as well as their photophysical and photochemical properties, the authors discuss in detail the major concepts of artificial photosynthesis and mechanisms of hydrogen production and water oxidation with ruthenium in section two. The third section of the text covers biological properties and important medical applications of ruthenium complexes as therapeutic agents or in diagnostic imaging. Aimed at stimulating research in this active field, this is an invaluable information source for researchers in academia, health research institutes and governmental departments working in the field of organometallic chemistry, green and sustainable chemistry as well as medicine/drug discovery, while equally serving as a useful reference also for scientists in industry. Note de contenu : "* Karen J. Brewer (1961 - 2014): A Bright Star that Burned Out Far Too Soon * Coordination Chemistry of Ruthenium * Photophysics and Photochemistry * Artificial Photosynthesis * Ruthenium-Containing Complexes with Cobalt and Hydrogenases for Hydrogen Production * Ligand Photosubstitution Reactions with Ruthenium Compounds: Applications in Chemical Biology and Medicinal Chemistry * Ruthenium Complexes in Photodynamic Therapeutics: State of the Art and New Trends * Photodynamic Therapy in Medicine with Mixed-Metal/Supramolecular Complexes * From Ru(III) Plasma Protein Binding Agents to Targeted Tumor Delivery * Design Aspects of Ruthenium Complexes as DNA Probes and Phototherapeutics * Ruthenium-Based Anticancer Compounds: Insights into their Cellular Targeting and Mechanism of Action * Ruthenium Complexes in Imaging Applications * Biological Activity of Ruthenium Complexes with Anti-Bacterial and Anti-Malarial Drugs * Ruthenium Complexes as NO Donors. Perspectives and Photobiological Applications * Trends and Future Developments of Ruthenium Anticancer Compounds * Ruthenium Complexes as Anti-Fungal Agents". Cote : B-D210 Num_Inv : 703 Localisation : LCC (SdS) Ruthenium complexes : Photomedical and biomedical applications [texte imprimé] / Holder, Alvin A., Auteur ; Lilge, Lothar, Auteur ; Browne, Wesley R., Auteur ; Lawrence, Mark A. W., Auteur ; Bullock Jr., Jimmie L., Auteur . - New York : Wiley, 2018 . - xx, 324 p. ISBN : 978-3-527-33957-0 Langues : Anglais (eng) Catégories : Chimie de coordination, Chimie organométallique, Métaux de transition Tags : RUTHENIUM Index. décimale : B-D Résumé : Edited by a team of highly respected researchers combining their expertise in chemistry, physics, and medicine, this book focuses on the use of rutheniumcontaining complexes in artificial photosynthesis and medicine. Following a brief introduction to the basic coordination chemistry of ruthenium complexes and their synthesis in section one, as well as their photophysical and photochemical properties, the authors discuss in detail the major concepts of artificial photosynthesis and mechanisms of hydrogen production and water oxidation with ruthenium in section two. The third section of the text covers biological properties and important medical applications of ruthenium complexes as therapeutic agents or in diagnostic imaging. Aimed at stimulating research in this active field, this is an invaluable information source for researchers in academia, health research institutes and governmental departments working in the field of organometallic chemistry, green and sustainable chemistry as well as medicine/drug discovery, while equally serving as a useful reference also for scientists in industry. Note de contenu : "* Karen J. Brewer (1961 - 2014): A Bright Star that Burned Out Far Too Soon * Coordination Chemistry of Ruthenium * Photophysics and Photochemistry * Artificial Photosynthesis * Ruthenium-Containing Complexes with Cobalt and Hydrogenases for Hydrogen Production * Ligand Photosubstitution Reactions with Ruthenium Compounds: Applications in Chemical Biology and Medicinal Chemistry * Ruthenium Complexes in Photodynamic Therapeutics: State of the Art and New Trends * Photodynamic Therapy in Medicine with Mixed-Metal/Supramolecular Complexes * From Ru(III) Plasma Protein Binding Agents to Targeted Tumor Delivery * Design Aspects of Ruthenium Complexes as DNA Probes and Phototherapeutics * Ruthenium-Based Anticancer Compounds: Insights into their Cellular Targeting and Mechanism of Action * Ruthenium Complexes in Imaging Applications * Biological Activity of Ruthenium Complexes with Anti-Bacterial and Anti-Malarial Drugs * Ruthenium Complexes as NO Donors. Perspectives and Photobiological Applications * Trends and Future Developments of Ruthenium Anticancer Compounds * Ruthenium Complexes as Anti-Fungal Agents". Cote : B-D210 Num_Inv : 703 Localisation : LCC (SdS)

Exemplaires(1)

Code-barres	Cote	Support	Localisation	Section	Disponibilité
703	B-D210	Texte imprimé	Bibliothèque	Livre	Disponible

Ruthenium in organic synthesis

Public ISBD Titre : Ruthenium in organic synthesis Type de document : texte imprimé Auteurs : Shun-Ichi Murahashi, Éditeur scientifique Editeur : Weinheim : Wiley-VCH Année de publication : 2004 Importance : xv, 383 p. Présentation : ill. Format : 25 cm ISBN/ISSN/EAN : 978-3-527-30692-3 Langues : Anglais (eng) Catégories : Chimie de coordination, Chimie organométallique, Métaux de transition Tags : RUTHENIUM  ORGANIC COMPOUNDS-Synthesis  ORGANOMETALLIC CHEMISTRY Index. décimale : B-D Résumé : "In this comprehensive book, one of the leading experts, Shun-Ichi Murahashi, presents all the important facets of modern synthetic chemistry using Ruthenium, ranging from hydrogenation to metathesis. In 14 contributions, written by an international authorship, readers will find all the information they need about this fascinating and extraordinary chemistry. The result is a high quality information source and a indispensable reading for everyone working in organometallic chemistry." Cote : B-D180 (SdS) Num_Inv : 3025 Ruthenium in organic synthesis [texte imprimé] / Shun-Ichi Murahashi, Éditeur scientifique . - Weinheim : Wiley-VCH, 2004 . - xv, 383 p. : ill. ; 25 cm. ISBN : 978-3-527-30692-3 Langues : Anglais (eng) Catégories : Chimie de coordination, Chimie organométallique, Métaux de transition Tags : RUTHENIUM  ORGANIC COMPOUNDS-Synthesis  ORGANOMETALLIC CHEMISTRY Index. décimale : B-D Résumé : "In this comprehensive book, one of the leading experts, Shun-Ichi Murahashi, presents all the important facets of modern synthetic chemistry using Ruthenium, ranging from hydrogenation to metathesis. In 14 contributions, written by an international authorship, readers will find all the information they need about this fascinating and extraordinary chemistry. The result is a high quality information source and a indispensable reading for everyone working in organometallic chemistry." Cote : B-D180 (SdS) Num_Inv : 3025

Exemplaires(1)

Code-barres	Cote	Support	Localisation	Section	Disponibilité
3025	B-D180	Texte imprimé	Bibliothèque	Livre	Disponible

Ruthenium silane and germane complexes : synthesis, electrochemical and catalytic studies / Smart, Katharine  

Public ISBD Titre : Ruthenium silane and germane complexes : synthesis, electrochemical and catalytic studies Type de document : texte imprimé Auteurs : Smart, Katharine, Auteur ; Grellier, Mary, Directeur de thèse ; Sylviane Sabo-Etienne, Directeur de thèse Année de publication : 2013 Langues : Anglais (eng) Tags : RUTHENIUM  SILANE  GERMANE  SILAZANE  DEUTERATION  ELECTROCHEMISTRY  NEUTRON DIFFRACTION  CATALYSIS Résumé : "The activation of E - H bonds (E = Si, Ge, H) by ruthenium complexes is subjected to detailed study. The first chapter describes the preparation of novel N-heterocycle-silane compounds, their employment as ligands to ruthenium and the properties of the resulting complexes. Several classes of ruthenium-N-heterocycle-silane species were isolated including a series bearing the motif RuSi3H comprising heptacoordinated moieties with three N-heterocycle-silane ligands and a hydride. As explored in chapter 2, two degenerate systems are encountered for RuSi3H; with the hydride located equidistant from the three silicon atoms or with the hydride closer to two silicon atoms than the third. Protonation of RuSi3H led to RuSi3H2+ bearing hydride, silyl and ??-(H??Si) ligands. In chapter 3, the wide range in oxidation potentials of the RuSi3H complexes is correlated to the electronic properties of the ligands. Chemical and electrochemical oxidation of a RuSi3H species gave rise to RuSi3H2+ and possible routes accounting for the transformation are examined. The focus shifts in chapter 4 to the activation of Ge - H bonds. Complexes of the type Ru(diphosphine)2(GeH3)(H) were accessed by the photochemical reaction of GeH4 with Ru(diphosphine)2H2. Study of germane systems continued with the reaction of Ph2GeH2 and the polyhydride complex Ru(H)2(?2-H2)2(PCy3)2 giving rise to a unique dihydrogen-germylene-ruthenium complex, Ru(H)2(=GePh2)(?2-H2)(PCy3)2. It was also possible to prepare (Ph2HGe)2O from the coupling of Ph2GeH2 and water in the presence of a catalytic amount of ruthenium. The complex Ru(H)4{(Ph2Ge)2O}(PCy3)2 was also isolated and identified as a key intermediate in the generation of (Ph2HGe)2O. The final chapter describes the selective catalytic deuteration of hydridosilanes with deuterium gas. It was possible to achieve the successful deuteration of a range of silanes with very low catalyst loading." Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse 3 Date_soutenance : 11/10/2013 Ecole_doctorale : Sciences de la matière (SdM) Domaine : Chimie Organométallique et de Coordination En ligne : http://thesesups.ups-tlse.fr/2186/ Ruthenium silane and germane complexes : synthesis, electrochemical and catalytic studies [texte imprimé] / Smart, Katharine, Auteur ; Grellier, Mary, Directeur de thèse ; Sylviane Sabo-Etienne, Directeur de thèse . - 2013. Langues : Anglais (eng) Tags : RUTHENIUM  SILANE  GERMANE  SILAZANE  DEUTERATION  ELECTROCHEMISTRY  NEUTRON DIFFRACTION  CATALYSIS Résumé : "The activation of E - H bonds (E = Si, Ge, H) by ruthenium complexes is subjected to detailed study. The first chapter describes the preparation of novel N-heterocycle-silane compounds, their employment as ligands to ruthenium and the properties of the resulting complexes. Several classes of ruthenium-N-heterocycle-silane species were isolated including a series bearing the motif RuSi3H comprising heptacoordinated moieties with three N-heterocycle-silane ligands and a hydride. As explored in chapter 2, two degenerate systems are encountered for RuSi3H; with the hydride located equidistant from the three silicon atoms or with the hydride closer to two silicon atoms than the third. Protonation of RuSi3H led to RuSi3H2+ bearing hydride, silyl and ??-(H??Si) ligands. In chapter 3, the wide range in oxidation potentials of the RuSi3H complexes is correlated to the electronic properties of the ligands. Chemical and electrochemical oxidation of a RuSi3H species gave rise to RuSi3H2+ and possible routes accounting for the transformation are examined. The focus shifts in chapter 4 to the activation of Ge - H bonds. Complexes of the type Ru(diphosphine)2(GeH3)(H) were accessed by the photochemical reaction of GeH4 with Ru(diphosphine)2H2. Study of germane systems continued with the reaction of Ph2GeH2 and the polyhydride complex Ru(H)2(?2-H2)2(PCy3)2 giving rise to a unique dihydrogen-germylene-ruthenium complex, Ru(H)2(=GePh2)(?2-H2)(PCy3)2. It was also possible to prepare (Ph2HGe)2O from the coupling of Ph2GeH2 and water in the presence of a catalytic amount of ruthenium. The complex Ru(H)4{(Ph2Ge)2O}(PCy3)2 was also isolated and identified as a key intermediate in the generation of (Ph2HGe)2O. The final chapter describes the selective catalytic deuteration of hydridosilanes with deuterium gas. It was possible to achieve the successful deuteration of a range of silanes with very low catalyst loading." Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse 3 Date_soutenance : 11/10/2013 Ecole_doctorale : Sciences de la matière (SdM) Domaine : Chimie Organométallique et de Coordination En ligne : http://thesesups.ups-tlse.fr/2186/

Complexes du ruthénium comportant un ligand dihydrogène étiré. Propriétés spectroscopiques et application à l'activation de liaisons carbonène-hydrogène / Guari, Yannick  

Public ISBD Titre : Complexes du ruthénium comportant un ligand dihydrogène étiré. Propriétés spectroscopiques et application à l'activation de liaisons carbonène-hydrogène Type de document : texte imprimé Auteurs : Guari, Yannick, Auteur ; Bruno Chaudret, Directeur de thèse Année de publication : 1998 Langues : Français (fre) Tags : RUTHENIUM  COMPLEXES DIHYDROGÈNE  DIHYDROGÈNE ÉTIRÉ  COUPLAGE D’ÉCHANGE QUANTIQUE  ACTIVATION C-H  CATALYSE HOMOGÈNE  COUPLAGE C-C Résumé : "Une série de complexes hydruro(dihydrogène) dont le ligand dihydrogène est étiré a été obtenue à partir du complexe RuH2(H2)2(PCy3)2 1 ou à partir de Ru (COD)(COT). Leurs synthèses et leurs caractérisations, la description de leurs propriétés spectroscopiques ainsi que leur réactivité et leur activité catalytique sont donnés dans ce mémoire. Le chapitre I est une mise au point bibliographique sur l'activation de liaisons carbone-hydrogène en milieu homogène. Le chapitre II est consacré à la synthèse et à la caractérisation de complexes hydruro(dihydrogène) du ruthénium (II), comportant deux ligands phosphine en position trans et un ligand chélatant orthométallé. Le complexe RuH(pyph)(H2) (PiPr3)2 présente en RMN des couplages d'échange quantique qui n'avaient jusqu'alors jamais été observes pour un complexe hydruro(dihydrogène). Nous détaillons l'étude de ces couplages d'échange au cours du chapitre III. La réactivité de ce complexe vis-à-vis de CO, N2 et O2 est donnée au cours de ce même chapitre. Nous présentons dans le chapitre IV la réactivité inhabituelle des complexes RuH(pyX)(H2) (PCy3)2 (X = O, NH) et RuH (quO)(H2) (PCy3)2 vis-à-vis du triéthylvinylsilane pour donner les complexes hydruro(vinylidène) correspondants. La mise en évidence spectroscopique d'interactions de type liaison hydrogène entre l'hydrure du complexe RuH(pyO)(H2) (PCy3)2 et le proton de différents alcools est également discutée ainsi que l'influence de cette liaison sur sa réactivité. Nous décrivons également au cours de ce chapitre l'utilisation du complexe 1 comme catalyseur pour le couplage de liaisons carbone-carbone entre l'éthylène et l'acétophénone ou la benzophénone en position ortho du groupement phényle. Les conditions expérimentales utilisées ainsi que le mécanisme réactionnel sont discutés. Le dernier chapitre est consacré aux essais exploratoires effectués à l'aide des deux complexes bis(dihydrogène) 1 et Tp*RuH(H2)2 pour l'activation d'alcanes." Document : Thèse de doctorat Etablissement_delivrance : Université de Toulouse 3 Date_soutenance : 05/10/1998 Domaine : Chimie Organométallique Localisation : LCC En ligne : http://www.theses.fr/1998TOU30209 Complexes du ruthénium comportant un ligand dihydrogène étiré. Propriétés spectroscopiques et application à l'activation de liaisons carbonène-hydrogène [texte imprimé] / Guari, Yannick, Auteur ; Bruno Chaudret, Directeur de thèse . - 1998. Langues : Français (fre) Tags : RUTHENIUM  COMPLEXES DIHYDROGÈNE  DIHYDROGÈNE ÉTIRÉ  COUPLAGE D’ÉCHANGE QUANTIQUE  ACTIVATION C-H  CATALYSE HOMOGÈNE  COUPLAGE C-C Résumé : "Une série de complexes hydruro(dihydrogène) dont le ligand dihydrogène est étiré a été obtenue à partir du complexe RuH2(H2)2(PCy3)2 1 ou à partir de Ru (COD)(COT). Leurs synthèses et leurs caractérisations, la description de leurs propriétés spectroscopiques ainsi que leur réactivité et leur activité catalytique sont donnés dans ce mémoire. Le chapitre I est une mise au point bibliographique sur l'activation de liaisons carbone-hydrogène en milieu homogène. Le chapitre II est consacré à la synthèse et à la caractérisation de complexes hydruro(dihydrogène) du ruthénium (II), comportant deux ligands phosphine en position trans et un ligand chélatant orthométallé. Le complexe RuH(pyph)(H2) (PiPr3)2 présente en RMN des couplages d'échange quantique qui n'avaient jusqu'alors jamais été observes pour un complexe hydruro(dihydrogène). Nous détaillons l'étude de ces couplages d'échange au cours du chapitre III. La réactivité de ce complexe vis-à-vis de CO, N2 et O2 est donnée au cours de ce même chapitre. Nous présentons dans le chapitre IV la réactivité inhabituelle des complexes RuH(pyX)(H2) (PCy3)2 (X = O, NH) et RuH (quO)(H2) (PCy3)2 vis-à-vis du triéthylvinylsilane pour donner les complexes hydruro(vinylidène) correspondants. La mise en évidence spectroscopique d'interactions de type liaison hydrogène entre l'hydrure du complexe RuH(pyO)(H2) (PCy3)2 et le proton de différents alcools est également discutée ainsi que l'influence de cette liaison sur sa réactivité. Nous décrivons également au cours de ce chapitre l'utilisation du complexe 1 comme catalyseur pour le couplage de liaisons carbone-carbone entre l'éthylène et l'acétophénone ou la benzophénone en position ortho du groupement phényle. Les conditions expérimentales utilisées ainsi que le mécanisme réactionnel sont discutés. Le dernier chapitre est consacré aux essais exploratoires effectués à l'aide des deux complexes bis(dihydrogène) 1 et Tp*RuH(H2)2 pour l'activation d'alcanes." Document : Thèse de doctorat Etablissement_delivrance : Université de Toulouse 3 Date_soutenance : 05/10/1998 Domaine : Chimie Organométallique Localisation : LCC En ligne : http://www.theses.fr/1998TOU30209

Development of ruthenium nanoparticles as catalyst models for the splitting of water : combination of experimental and theoretical chemistry approaches / Gonzalez Gomez, Roberto  

Public ISBD Titre : Development of ruthenium nanoparticles as catalyst models for the splitting of water : combination of experimental and theoretical chemistry approaches Type de document : texte imprimé Auteurs : Gonzalez Gomez, Roberto, Auteur ; Karine Philippot, Directeur de thèse ; Poteau, Romuald, Directeur de thèse Année de publication : 2019 Langues : Anglais (eng) Tags : RUTHENIUM  NANOPARTICLES  ORGANOMETALLIC CHEMISTRY  COORDINATION CHEMISTRY  DFT TITRATION  SURFACE MAPPING  LIGAND EXCHANGE  HYDROGEN  CATALYSIS  WATER SPLITTING Résumé : "This PhD thesis is an upstream study regarding the production of hydrogen (H2) via the water splitting process. The reactions involved (water oxidation, WOR and hydrogen evolution reactions, HER) require efficient catalysts and nanoparticles (NPs) can act so. Such catalysis can be photoactivated by combining photosensitizers (PS) with the NPs leading to hybrid PS-NPs systems, and effective assembling is able via carboxylic acid groups. This work relies on a combination of experimental and theoretical tools to develop novel ruthenium-based nanocatalysts for the water splitting process. Our contribution aimed at achieving a precise mapping of the surface of ruthenium nanoparticles (RuNPs) stabilized by carboxylic acids with an alkyl chain of different length as model systems for the design of PS-NPs catalysts for H2 photoproduction from water. One of the main aims of this PhD was to bring a better understanding of structure/properties relationship at the nanoscale to explain the surface properties of RuNPs stabilized by carboxylic acids and their catalytic viability. RuNPs were synthesized by the organometallic approach using the [Ru(COD)(COT)] complex as metal source and ethanoic, pentanoic and octanoic acids as stabilizers. This synthesis method allows the formation of well-controlled metal NPs, thus providing nanosystems of choice for fine comparative studies. TEM characterization revealed the formation of homogeneous populations of RuNPs in a size range of 1.1 - 1.7 nm. The surface state of the NPs was probed by complementary analytical techniques like IR, NMR and WAXS, leading to a precise mapping of their surface. Optimization studies of the ligand/[Ru] ratio to get NPs with a similar size allowed to have comparable nanosystems whatever the carboxylic acid used as stabilizer and thus to determine the influence of the alkyl chain length. DFT calculations were performed in parallel according to a thermodynamic model fed with DFT energies. Also, a systematic analysis of the bond properties and of the electronic states (Density of States, Crystal Orbital Hamilton Population, atomic charges) was carried out using a Ru55 NP model. DFT calculations of the vibrational features of model RuNPs and of the chemical shifts of model Ru clusters also allowed to secure the spectroscopic experimental assignations. Spectroscopic data and DFT mechanistic studies evidenced that the carboxylic acids lie on the metal surface as carboxylates, together with hydrogen atoms. The results of experimental and theoretical titrations are in good agreement, thus showing the approach followed to be an efficient step to build a model in order to understand the ligand influence on RuNPs properties. Hydrogen adsorption Gibbs free energy, which is a reference parameter to determine the viability of materials for HER catalysis, has been calculated for optimized RuNP structures. The best nanocatalyst revealed to have both, intermediate crowded metal surface and intermediate alkyl chain length for the capping ligand, indicating the RuNPs stabilized by pentanoic acid as the most promising catalyst. Experiments on ligand exchange at the surface of octanoic acid-stabilized RuNPs were also performed in order to model the PS anchoring onto RuNPs through carboxylic acid groups completed by theoretical studies. Results obtained demonstrated the potentiality of this approach. The originality of this work lies with the combination of experimental and theoretical studies in parallel to achieve a better understanding of structure/properties relationship of RuNPs stabilized by carboxylic acids and their catalytic viability for the water-splitting process. Preliminary catalytic results are encouraging, and the data obtained should now allow to design appropriate nanocatalysts. Finally, the interest of this combined approach has been demonstrated through the study of RuNPs for water splitting, but this work opens new opportunities of research in nanocatalysis." Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse 3 Date_soutenance : 11/04/2019 Ecole_doctorale : Sciences de la Matière (SdM) (Toulouse) Domaine : Chimie Organométallique et de Coordination Localisation : LCC En ligne : https://theses.hal.science/tel-02314066 Development of ruthenium nanoparticles as catalyst models for the splitting of water : combination of experimental and theoretical chemistry approaches [texte imprimé] / Gonzalez Gomez, Roberto, Auteur ; Karine Philippot, Directeur de thèse ; Poteau, Romuald, Directeur de thèse . - 2019. Langues : Anglais (eng) Tags : RUTHENIUM  NANOPARTICLES  ORGANOMETALLIC CHEMISTRY  COORDINATION CHEMISTRY  DFT TITRATION  SURFACE MAPPING  LIGAND EXCHANGE  HYDROGEN  CATALYSIS  WATER SPLITTING Résumé : "This PhD thesis is an upstream study regarding the production of hydrogen (H2) via the water splitting process. The reactions involved (water oxidation, WOR and hydrogen evolution reactions, HER) require efficient catalysts and nanoparticles (NPs) can act so. Such catalysis can be photoactivated by combining photosensitizers (PS) with the NPs leading to hybrid PS-NPs systems, and effective assembling is able via carboxylic acid groups. This work relies on a combination of experimental and theoretical tools to develop novel ruthenium-based nanocatalysts for the water splitting process. Our contribution aimed at achieving a precise mapping of the surface of ruthenium nanoparticles (RuNPs) stabilized by carboxylic acids with an alkyl chain of different length as model systems for the design of PS-NPs catalysts for H2 photoproduction from water. One of the main aims of this PhD was to bring a better understanding of structure/properties relationship at the nanoscale to explain the surface properties of RuNPs stabilized by carboxylic acids and their catalytic viability. RuNPs were synthesized by the organometallic approach using the [Ru(COD)(COT)] complex as metal source and ethanoic, pentanoic and octanoic acids as stabilizers. This synthesis method allows the formation of well-controlled metal NPs, thus providing nanosystems of choice for fine comparative studies. TEM characterization revealed the formation of homogeneous populations of RuNPs in a size range of 1.1 - 1.7 nm. The surface state of the NPs was probed by complementary analytical techniques like IR, NMR and WAXS, leading to a precise mapping of their surface. Optimization studies of the ligand/[Ru] ratio to get NPs with a similar size allowed to have comparable nanosystems whatever the carboxylic acid used as stabilizer and thus to determine the influence of the alkyl chain length. DFT calculations were performed in parallel according to a thermodynamic model fed with DFT energies. Also, a systematic analysis of the bond properties and of the electronic states (Density of States, Crystal Orbital Hamilton Population, atomic charges) was carried out using a Ru55 NP model. DFT calculations of the vibrational features of model RuNPs and of the chemical shifts of model Ru clusters also allowed to secure the spectroscopic experimental assignations. Spectroscopic data and DFT mechanistic studies evidenced that the carboxylic acids lie on the metal surface as carboxylates, together with hydrogen atoms. The results of experimental and theoretical titrations are in good agreement, thus showing the approach followed to be an efficient step to build a model in order to understand the ligand influence on RuNPs properties. Hydrogen adsorption Gibbs free energy, which is a reference parameter to determine the viability of materials for HER catalysis, has been calculated for optimized RuNP structures. The best nanocatalyst revealed to have both, intermediate crowded metal surface and intermediate alkyl chain length for the capping ligand, indicating the RuNPs stabilized by pentanoic acid as the most promising catalyst. Experiments on ligand exchange at the surface of octanoic acid-stabilized RuNPs were also performed in order to model the PS anchoring onto RuNPs through carboxylic acid groups completed by theoretical studies. Results obtained demonstrated the potentiality of this approach. The originality of this work lies with the combination of experimental and theoretical studies in parallel to achieve a better understanding of structure/properties relationship of RuNPs stabilized by carboxylic acids and their catalytic viability for the water-splitting process. Preliminary catalytic results are encouraging, and the data obtained should now allow to design appropriate nanocatalysts. Finally, the interest of this combined approach has been demonstrated through the study of RuNPs for water splitting, but this work opens new opportunities of research in nanocatalysis." Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse 3 Date_soutenance : 11/04/2019 Ecole_doctorale : Sciences de la Matière (SdM) (Toulouse) Domaine : Chimie Organométallique et de Coordination Localisation : LCC En ligne : https://theses.hal.science/tel-02314066

Controlled synthesis and characterization of ru-fullerene nanostructures and their catalytic applications / Faqiang Leng  

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Coordination de boranes originaux en chimie du Ru et de l'Ir. Complexes bis-sigma-boranes, borohydrures, boryles, et B-H agostiques / Gloaguen, Yann  

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Ligands ambiphiles pyridine / borane et phosphine / borane : synthèse, structure, coordination et réactivité / Vergnaud, Jérôme  

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