Nowadays, catalysis lies at the heart of economy growth mainly in the petroleum industry. Catalysis can offer real and potential solutions to the current challenges for a long-term sustainable energy, green chemistry, and environmental protection. In this context, one of the most important and future prosperity promising catalytic applications in the petrochemical field is hydrocarbons metathesis; it consists on the conversion of both renewable and non-petroleum fossil carbon sources to transportation fuels. Olefin metathesis has become one of the standard methodologies for constructing C-C bonds in many organic transformation reactions. This owed to the numerous types of metathesis reactions that have been developed, for example, enyne, ring-opening and closing, self and cross metathesis, etc. But the one step conversion of olefin to alkanes has not been studied much. Recently, only one such a work has been published for the hydro-metathesis of propylene by tantalum hydride supported on KCC-1 in dynamic reactor. With this knowledge, we thought to study the hydro-metathesis using liquid olefin (1-decene). Another aspect of using 1-decene comes from our previous experience on metathesis of n-decane where the first step is the conversion of decane to 1-decene and subsequently to different chain length alkanes with W-alkyl/alkylidene catalyst. In this way, it would be easy for us to use different catalysts and compare them with parent catalyst concerning TON. We found 100% conversion with TON of 1010 using supported WMe6 onto SiO2-700 [(≡Si-O-)WMe5] against the previous results for n-decane showing 20% conversion and TON of 153. In this work, we disclose the hydro-metathesis reaction of 1-decene using well-defined silica supported W(VI), Mo(VI) and Ta(V) alkyl catalysts in batch reactor condition. This work is divided into three major sections; first chapter contains an introduction to the field of catalysis and surface organometallic chemistry. In second chapter, we describe all the experimental procedures of the catalysts. The third chapter is devoted to the characterization and interpretation followed by catalytic reactions. Finally, a brief conclusion of the present study is given.

Stable dinuclear complexes bis(heptane-2,4,6-trionato)dicopper(II) [Cu2(daa)2], bis(1,5-diphenyl-1,3,5-pentanetrionato)dicopper(II) [Cu2(dba)2], bis(1,5-diphenyl-1,3,5-pentanetrionato)dicobalt(II) [Co2(dba)2], and [6,11-dimethyl-7,10-diazahexadeca-5,11-diene-2,4,13,15-tetranato(4-)-N7N10O4O13;O2O4O13O15] copper(II)cobalt(II) [(CuCo(daaen)] were supported on Cab-O-Sil by the batch impregnation technique. The supported samples were characterized by UV-Vis, elemental analysis, X-ray powder diffraction (XRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and thermal gravimetric analysis (TGA). Elemental analysis and TGA data confirm that the Cu2(daa)2 complex loses one of its coordinated ligands upon adsorption onto silica in THF at greater than 4.43 wt% Cu loading. By contrast, at all Cu loadings the Cu2(dba)2 complex was adsorbed on the silica surface in CH2Cl2 without loss of ligand. XRD and DRIFTS results confirmed the formation of Cu2(dba)2 multilayer films on the Cab-O-Sil surface for samples containing greater than 2.64 wt% copper. The dinuclear cobalt complex and copper-cobalt complex also do not lose their coordination ligands upon adsorption on the surface. These two metal complexes are amorphous and did not produce XRD patterns. However, DRIFTS results confirm that the binuclear cobalt complex and the copper-cobalt complex begin forming multilayer films between 1.21and 2.53 wt% Cu. The Cu2(dba)2/silica precatalysts were subsequently converted to the catalysts by decomposing the organic ligands at 450 degrees Celsius followed by activation with 2% H2 at 250 degrees Celsius and were evaluated for methanol synthesis and methanol decomposition reactions. Kinetic studies demonstrated that the 3.70% Cu/silica[Cu2(dba)2] catalyst is more active for methanol decomposition than it is for methanol synthesis. The supported dinuclear cobalt and copper-cobalt precatalysts were converted to the catalyst by heating at 450 degrees Celsius followed by activation of the catalysts with 50% H2. Four different catalysts, 3.5% Co/silica[Co2(dba)2], 6.7% Co/silica[Co2(dba)2], 2.3% Co/silica[CuCo(daaen)], and 5.5% Co/silica[Co2(daa)2] were evaluated for the Fischer-Tropsch reaction at 350 degrees Celsius in a batch reactor. The supported binuclear cobalt catalyst produced C1-C7 alkanes and a significant amount of CO2. By contrast, the catalyst formed from heterobinuclear CuCo(daaen) showed the ability to convert syngas to aromatics with a narrow product distribution. In addition, the 6.7% Co/silica[Co2(dba)2] multilayer catalysts have above 98% conversion rates and 60% liquid hydrocarbon selectivity in a flow reactor.

Aliphatic polyesters such as polycaprolactone and polylactide have received more attention in recent years for their use in biomedical applications because of their biodegradable nature. These polymers are often synthesized using homogeneous metal complexes. Unfortunately, using homogeneous metals as catalysts leads to metal contamination in the product polymer, a result which is highly undesirable in a polymer intended for biomedical use. More recent work has shown that these polymers can be synthesized using homogeneous metal-free complexes. These catatlysts are generally less active than metal catalysts, and although they do not contaminate the polymer with metal residue, they are still difficult to recover and hence recycle for further use. In this work, we attempted to create a metal-free, silica-supported catalyst for use in the synthesis of polycaprolactone or polylactide. Ultimately, n-propylsulfonic acid-functionalized porous and nonporous silica materials are evaluated in the ring-opening polymerization of epsilon-caprolactone. All catalysts allow for the controlled polymerization of the monomer, producing polymers with controlled molecular weights and narrow polydispersities. Polymerization rates are low, with site-time-yields generally one to three orders of magnitude lower than metal-based systems. The catalysts are easily recovered from the polymerization solution after use and are shown to contain significant residual adsorbed polymer. Solvent extraction techniques are useful for removing most of the polymer, although the extracted solids are not effective catalysts in recycle experiments. These new materials represent a green alternative to traditional metal-based catalysts, as they are recoverable and leave no metal residues in the polymer.

Several ligands derived from D-glucosamine, designed for different catalytic reactions havebeen synthesized. The ligands for homogeneous catalysis based on 1,2-glucodiamine wereprepared, and used in reactions of allylic alkylation, hydrogenation and Michael addition.Supported Aqueous Phase Catalyst (SAPC) system was prepared from D-glucosamine anduse with very good results in Suzuki Miyaura cross coupling reactions. Catalyst was alsorecycled. Attempt to prepare ligands grafted on SBA-silica matrix were made as well asligands containing poly(ethylene) glycol moiety.

Im Rahmen der vorliegenden Arbeit wurde eine neuartige Methode und die entsprechenden Katalysatoren für die heterogen katalysierte Gasphasen-Epoxidation von Propen entwickelt und optimiert. Das Propen wurde an FeOx/SiO2-Katalysatoren mit N2O als Oxidationsmittel epoxidiert. Die Katalysatoren wurden mittels XRD, TEM, XPS, Physi- und Chemisorption, TPR/TPO, TPD und IR untersucht und charakterisiert. Der Einfluß der Reaktionsbedingungen auf die Oxidationsergebnisse wurde bestimmt und Untersuchungen zum Reaktionsablauf durchgeführt. Es wurden Selektivitäten zu Propenoxid von 40-70%, bei Propenumsätzen von 3-12%, erreicht. Die maximalen erzielten PO-Ausbeuten betrugen über 5%, und sind damit den berichteten Ergebnisse aus der Literatur überlegen.

Ce mémoire présente une méthodologie théorique pour comprendre l'origine de différence de comportement dynamique de complexes alkylidènes, catalyseurs de type Schrock de la métathèse des oléfines, greffés un support de silice amorphe. Dans un travail antérieur, les différences entre les valeurs de l'anisotropie de déplacement chimique (CSA) obtenus par des mesures de RMN du solide et celles estimées par le calcul pour des systèmes figés avaient conduit à suggérer des régimes dynamiques différents pour ces complexes, certains étant proposés comme immobiles, d'autres comme mobiles. Dans le premier groupe se trouve les complexes du molybdène et dans le second les complexes du tungstène, rhénium et tantale. Dans le cadre de cette thèse, nous nous sommes donc attachés à mettre en place une méthodologie pour déterminer ces CSA et donc la nature de la dynamique de chaque système qui conduit au CSA moyenné. Nous nous sommes d'abord intéressés à des systèmes moléculaires pour révéler des interactions non covalentes entre les complexes et le support silice à partir d'une approche de type petit cluster en utilisant divers niveaux de calculs DFT et modèles moléculaires. Cette modélisation moléculaire de la silice étant insuffisante, nous avons entrepris une modélisation de la surface de silice amorphe par dynamique moléculaire classique dont les caractéristiques ont été comparées aux données expérimentales existantes. Le comportement dynamique de ces systèmes greffés sur silice amorphe a été simulé par dynamique moléculaire ab initio QM/MM, couplant une description quantique du complexe organométallique à une description classique du support. Ces études dynamiques ont conduit à des valeurs de CSA moyennées dans le temps de la dynamique. La comparaison de ces valeurs calculées et des valeurs expérimentales a permis d'apporter des éléments de réponse sur l'origine des différences de comportement dynamique de ces complexes alkylidènes. De façon remarquable des mouvements d'ensemble des espèces greffées par rapport à la surface de silice et des modifications de la coordination du métal par l'apparition d'interaction agostique contribuent à moyenner le CSA. / This work presents a theoretical study aimed at analyzing the origin of the differences in the dynamics of alkylidenes complexes, known as Schrock olefin metathesis catalysts, supported on amorphous silica. The difference between the experimental chemical shift anisotropies (CSA) obtained from solid state NMR measurements and the values computed for the most stable configurations have been used in previous work to suggest different dynamical behaviors for the supported complexes. Some of the complexes were suggested to have limited mobilities while others were suggested to be mobiles. In the first group, one finds Mo complexes, and in the second, W, Re and Ta complexes. In this thesis, a methodology was established to compute the CSA and to obtain information on the dynamics that average the CSA over time. In the first part of this work, molecular species were considered and the non covalent interactions between the surface and the grafted complexes were studied with various DFT levels of calculations and various molecular models. This molecular modeling being inappropriate, a better representation of the surface of amorphous silica was carried out with classical molecular dynamic methods. The nature of the surface was analyzed and compared with available experimental information. In a following step, the dynamic behavior of these complexes was determined using anab initio molecular dynamics (QM/MM) approach in which the metal fragments are treated at the quantum level and the support represented in a classical manner. These molecular dynamics studies yield time averaged CSA that are reasonably close to the experimental values and confirm in particular the partition into immobile (Mo) and mobile (W, Re, Ta) complexes. A detailed analysis of the results leads to a better understanding of the nature of the dynamics. Remarkably, motions relative to the silica surface and vibrations influencing the coordination sphere of the metal involving in particular agostic interactions both contribute to average the CSA.

Plusieurs ligands dérivés de la D-glucosamine, conçus pour différentes réactions catalytiques,ont été synthétisés. Les ligands pour la catalyse homogène basés sur 1,2-glucodiamine ontété préparés, et utilisés dans des réactions d'alkylation allylique, d'hydrogénation et d'additionde Michael.La D-glucosamine a utilisee pour la preparation de catalysateur type de SPAC (SupportedAqueous Phase Catalyst). Ce catalysateur hétérogène été utilisé avec de très bons résultatsdans les réactions de couplage croisé de Suzuki Miyaura. Le catalyseur a également étérecyclé. Des essais de préparation de ligands greffés sur une matrice de silice de type SBA-15ont été réalisés ainsi que des ligands à base de poly (éthylène) glycol. / Several ligands derived from D-glucosamine, designed for different catalytic reactions havebeen synthesized. The ligands for homogeneous catalysis based on 1,2-glucodiamine wereprepared, and used in reactions of allylic alkylation, hydrogenation and Michael addition.Supported Aqueous Phase Catalyst (SAPC) system was prepared from D-glucosamine anduse with very good results in Suzuki Miyaura cross coupling reactions. Catalyst was alsorecycled. Attempt to prepare ligands grafted on SBA-silica matrix were made as well asligands containing poly(ethylene) glycol moiety.

Im Rahmen der vorliegenden Arbeit wurde eine neuartige Methode und die entsprechenden Katalysatoren für die heterogen katalysierte Gasphasen-Epoxidation von Propen entwickelt und optimiert. Das Propen wurde an FeOx/SiO2-Katalysatoren mit N2O als Oxidationsmittel epoxidiert. Die Katalysatoren wurden mittels XRD, TEM, XPS, Physi- und Chemisorption, TPR/TPO, TPD und IR untersucht und charakterisiert. Der Einfluß der Reaktionsbedingungen auf die Oxidationsergebnisse wurde bestimmt und Untersuchungen zum Reaktionsablauf durchgeführt. Es wurden Selektivitäten zu Propenoxid von 40-70%, bei Propenumsätzen von 3-12%, erreicht. Die maximalen erzielten PO-Ausbeuten betrugen über 5%, und sind damit den berichteten Ergebnisse aus der Literatur überlegen.