En la primera part del present treball es presenta la investigació duta a terme sobre la reacció d'hidroesterificació d'olefines. S'analitzen els factors que afecten la reactivitat i quimioselectivitat de les reaccions d'hidroesterificació i deuterioesterificació en sistemes catalítics basats en complexes de pal·ladi amb lligands auxiliars de tipus fosfina. Es presenta un estudi detallat del mecanisme catalític a través del qual tenen lloc aquestes reaccions. La determinació del mecanisme de reacció ha estat aplicada a la obtenció d'una versió enantioselectiva de la mateixa. En una segona part del treball s'han analitzat diversos sistemes de modificació superficial de fibres naturals i el seu efecte sobre la compatibilitat fibra - matriu en materials compòsits de matriu poliolefínica. S'han caracteritzat les propietats superficials de fibres de pi químicament modificades. Les fibres naturals modificades s'han utilitzat en la preparació de materials compòsits, les propietats mecàniques, tèrmiques i termomecàniques dels quals han estat caracteritzades i analitzades. / The first part of the present work exposes the results obtained during the study of the reactions of hydro and deuterioesterification of acenaphthylene. The different parameters involved in the catalitic system based on palladium complexes with phosphines have been analyzed, allowing the determination of the reaction´s mechanism. This determination has allowed the development of an enantioselective version of this reaction.The second part deals with the chemical modification of natural fibres and their effect on the interface of natural fibre reinforced composites. The surface properties of chemically modified pine fibres have been analyzed throught several techniques. The interface compatibilization provided by such treatments has been analyzed thorough the study of the mechanical, thermal and thermomechanical properties of PP reinforced composites.

Nesta Dissertação, foram realizadas reações de copolimerização de 1,3-butadieno com diferentes alfa-olefinas (1-hexeno, 1-octeno e 1-dodeceno) utilizando-se um sistema catalítico do tipo Ziegler-Natta ternário constituído por versatato de neodímio, hidreto de diisobutilalumínio e cloreto de t-butila. O sistema catalítico também foi avaliado em reações de homopolimerização com cada alfa-olefina. As condições reacionais, tanto da síntese do catalisador como das reações de polimerização, foram mantidas constantes. Foi estudada a influência de diferentes teores de cada alfa-olefina (1, 3, 5, 10, 20 e 30 % em relação ao 1,3-butadieno) sobre a conversão da polimerização, a microestrutura, a massa molar, as propriedades viscosimétricas e a estabilidade térmica dos polímeros obtidos. Foi avaliada, ainda, a influência do tamanho da cadeia da alfa-olefina sobre as características da polimerização. Os polímeros foram caracterizados por espectroscopia na região do infravermelho (FTIR), cromatografia por exclusão de tamanho (SEC), viscosimetria capilar e termogravimetria (TG). A microestrutura dos polímeros, praticamente, não variou com a adição das alfa-olefinas. A massa molar numérica média (Mn) não sofreu alterações significativas, enquanto que a massa molar ponderal média (Mw) apresentou tendência ao aumento, quanto maior foi a incorporação de comonômero. A viscosidade intrínseca não apresentou uma tendência com a adição da alfa-olefina na reação, permanecendo na faixa de 2,015 a 3,557 dL/g. A estabilidade térmica do copolímero mostrou uma tendência a aumentar com a incorporação das alfa-olefinas / In this work, were performed copolymerization reactions of 1,3-butadiene with different alpha-olefins (1-hexene, 1-octene and 1-dodecene), using a ternary catalytic system of Ziegler-Natta, constituted by neodymium versatate, diisobutylaluminum hydride and t-butyl chloride. The catalytic system was also evaluated in homopolymerization reactions with the alpha-olefins. The reaction conditions, both the catalyst synthesis as the polymerization reactions, were kept constant. The influence of different content of each alpha-olefin (1, 3, 5, 10, 20 and 30% compared to 1,3-butadiene) on the polymerization conversion, the microstructure, molar mass, viscometric properties and thermal stability of polymers was studied. The influence of alpha-olefin chain size on polymerization characteristics was also evaluated. The polymers were characterized by infrared spectroscopy (FTIR), size exclusion chromatography (SEC), capillary viscometry and thermogravimetry (TG). The polymer microstructure, practically, did not change with the addition of alpha-olefins. The number average molecular mass (Mn) has not changed; while the weight average molecular mass (Mw) trended to increase. The intrinsic viscosity did not show a trend with the alpha-olefin addition, remaining in the range from 2.015 to 3.557 dL/g. The copolymer thermal stability showed a tendency to increase with the incorporation of alpha-olefins

La phase initiale (de quelque fractions de seconde à quelques minutes) de la polymérisation catalytique des oléfines est encore peu comprise. Elle est pourtant reconnue comme une étape cruciale pour contrôler la morphologie de la particule de polymère et pour garantir la performance optimale du catalyseur et une certaine stabilité thermique du procédé. Ce travail présente l'étude et l'optimisation d'un mini réacteur à lit fixe pour mener des polymérisations catalytiques en phase gaz avec des durées très faibles (minimum 0.1s) dans des conditions proches à celles utilisées industriellement. La possibilité de suivre la température du gaz et de récupérer les particules de polymère pour les caractériser permet de décrire d'une façon complète le comportement du catalyseur au début de la réaction. L'étude a été limitée à la polymérisation de l'éthylène (avec un catalyseur métallocène supporté sur silice) et l'attention a été particulièrement mise sur la relation entre transfert de chaleur de la particule et performance du catalyseur. Il a été montré que des températures trop élevées peuvent être responsable localement de la modification du comportement du site active et de l'altération des propriétés des polymères. Un choix adéquat des conditions de réaction permet de suivre indirectement l'évolution de la température des particules en mesurant celle de la phase gaz. Dans un deuxième temps différents métallocènes ont été utilisés pour étudier l'influence des conditions de réaction, de la préparation du catalyseur et des propriétés du support sur l'activité, les propriétés du polymère et la morphologie des particules au temps court. Une attention particulière a été portée sur l'évolution des sites actifs et sur la cristallisation des chaînes de polymère dans un support poreux en évolution. Une activité élevée a été mesurée dans les premières cinq secondes et les températures de fusion et cristallisation des polymères ont été utilisées comme sondes pour mesurer l'avancement de la fragmentation du support. Les résultats ainsi obtenus peuvent non seulement clarifier certains aspects clé du début de la polymérisation mais aussi être utilisés comme donnés de départ pour modéliser la particule en croissance et contribuer à réduire l'écart qui est actuellement présent entre comportement réel du catalyseur et prédictions des modèles / The early stages (from less than 1s to few minutes) of catalytic olefin polymerization are still fairly understood even if they are nowadays recognized to be crucial for the determination of the morphology of the polymer particle, the optimization of the whole catalyst performance and the thermal stability of the process. In this work we will present how we studied and optimized a specially conceived packed bed reactor to perform gas phase catalytic olefin polymerizations as short as 0.1s under industrially relevant conditions. The possibility to measure the reactor temperature and to recover unaltered the polymer particles allows to take a complete picture of the catalyst behavior at the reaction start-up. The study will be restrained to ethylene polymerization with silica supported metallocenes and special attention will be given to the relation between heat transfer from the growing particle and catalyst performance. It will be seen how particle temperature evolution can be followed indirectly by measuring the gas phase temperature .In the second part of this work different metallocene complexes will be used to study the influence of process conditions, catalyst preparation method and support properties on the evolution of reaction rate, and polymer MWD during the first reaction seconds. Special attention will be given to the active site evolution during the transient phase and it will be shown that temperature excursions can be responsible for a local variation in active site behavior thus altering the properties of the formed polymer. The last section will be dedicated to the study of the peculiar crystallization behavior of the polymer chains in an evolving inorganic support. It will be shown how the melting and crystallization temperatures of the polymers can be used as “sensors” to measure the degree of fragmentation of the support particle. The results obtained in this work allow to gain a deeper understanding of the key parameters for the polymerization start-up and can be used as input for single particle models thus allowing to reduce the gap actually present between real catalyst behavior and model predictions

In the adaptation to the oxidative environment on earth, metals played a crucial role for the evolution of life. The presence of metals also allowed access to advanced functions due to their unique coordination sphere and reactivity. This thesis focused on exploiting these unique properties for further development of the field of dynamic chemistry – a field in which adaptation plays a central role as well. The first part of the thesis aimed to create a better understanding of multivalent effects in carbohydrate-lectin interactions. By reversible ligand coordination to zinc ions one of the nanoplatforms, the Borromean rings, could be selectively obtained. After carbohydrate functionalization the binding events were monitored by quartz crystal microbalance technology and compared to glycosylated fullerenes and dodecaamide cages. Overall, this investigation indicated that statistical and polyelectrolyte effects play a considerable role in the observed multivalent effects. The second part of the thesis aimed to design and synthesize a new catalyst for application in aqueous olefin metathesis. This afforded a ruthenium based catalyst that was applied in the self- and cross-metathesis of highly functionalized substrates, such as carbohydrates. In addition, it was shown that addition of a small amount of acetic acid prevented undesired double bond isomerization. The last part of the thesis aimed to explore new methods to discover transition metal catalysts. Dynamic exchange of directing groups generated a pool of potential substrates for C-H activation. Combining this pool of substrates with a pool of potential catalysts resulted in amplification of a reactive substrate/metal combination. By iterative deconvolution in combination with mass spectrometry, this “intermediate” could be identified from the mixture, proving applicability of this alternative approach to catalyst discovery. / <p>QC 20170809</p>

The research goal of this work was dedicated to improvement of the properties and enhancement of the application potential of commodity polymer based on polyolefins by choosing different synthesis routes to create new structures and materials. More precisely, the presented study explores different aspects of metallocene and post-metallocene catalyzed olefin polymerization leading to synthesis of novel copolymers and nanocomposites. The first part of this thesis deals with controlled polymerization of α-olefins catalyzed by post-metallocenes. Bis(phenoxyamine) zirconium complexes with [ONNO]-type ligands bearing cumyl (bPA-c) and 1-adamantyl (bPA-a) ortho-substituents were applied. For the polymerization catalyzed by bPA catalyst quasi-living kinetic character is proposed. The bPA catalyst was applied for synthesis of block copolymers by employing the strategy of sequential monomer addition. The blocky structure of the copolymer was successfully achieved and confirmed by NMR techniques. Moreover, the monomodal distribution of molar mass in SEC chromatogram confirmed the absence of homopolymers. In the second part of the work new defined comb-like copolymers (CLC) having a poly(10-undecene-1-ol) (PUol) backbone and densely grafted poly(ε-caprolactone) (PCL) side chains are presented. These copolymers were synthesized in two steps by means of metallocene polymerization followed by ring opening polymerization. Copolymers with varied and adjustable graft length (PCL segments) were synthesized. It was proved that the melting and crystallization temperatures of the CLC correlate with the PCL side chain length, i.e. longer chains result in higher Tm and Tc,o values. The melting enthalpy was found to be asymptotically dependent on the length of PCL side chains. The bulk morphology of the comb-like copolymers is proposed to be lamellar as judged from the TEM micrographs. The third part of the thesis is focused on the synthesis of polypropylene nanocomposites via in situ polymerization. Thereby, organomodified aluminumphosphate with kanemite-type layered structure (AlPO-kan) has been used as novel filler. Melt compounding composites were prepared for comparison purposes to evaluate the influence of in situ synthesis on the dispersion quality of the filler in polymer matrix. Melt compounding of neat AlPO-kan with PP did not lead to formation of nanocomposites. TEM images show macro-composites with the lamellar solid remaining agglomerated. On the contrary, in situ polymerization of propene yielded materials with exfoliated nanocomposite morphology. In XRD, diffractions of the AlPO-kan pilling of layers are not detectable. It can be concluded that the primary existing layers are delaminated. Very fine distribution of the filler in the polypropylene matrix has been impressively demonstrated by TEM.

Le réacteur à inversion de flux pour retenir et recycler la chaleur est une technologie efficace qui intègre la réaction chimique et la réutilisation de la chaleur dégagée lors de la réaction. Cette technologie a été considérablement commercialisée et industrialisée, vue l'amélioration de la productivité du réacteur et vue l'intensification du procédé qu'elle offrirait. Par analogie chaleur-matière, il a été voulu, par l'actuel travail de doctorat, évaluer la technologie d'inversion de flux et la combinaison de la réaction chimique et de la séparation et la rétention du catalyseur (matière) dans un seul réacteur adsorbeur multifonctionnel. La métathèse des oléfines qui utilise des catalyseurs moléculaires -qui ne sont pas/ ne peuvent pas être efficacement et parfaitement immobilisés et hétérogénéisés sur un support solide- peut être réalisée dans le réacteur adsorbeur à inversion de flux, qui prétend permettre de séparer, de recycler et de retenir les catalyseurs. La réaction cible dans cette thèse est l'homo-métathèse de l'oléate de méthyle. D'abord, un modèle cinétique pour décrire cette réaction et la transformation du réactif a été développé et proposé en suivant une approche micro-cinétique. Ensuite, ce modèle a été ajusté par rapport aux résultats expérimentaux pour optimiser et accéder aux paramètres cinétiques de la réaction. Le modèle cinétique, ainsi obtenu, permettra après son intégration dans le modèle du réacteur adsorbeur à inversion de flux, de prédire la conversion du réactif et sa concentration à la sortie. Le réacteur adsorbeur à inversion de flux, a été étudié et évalué, par la modélisation et par une étude théorique calculatoire, pour avoir une meilleure compréhension de son comportement, et aussi de l'influence des conditions opératoires sur le procédé (perte de catalyseur, conversion, productivité, etc.). Le design de réacteur qui a été proposé dans cette étude et ce travail est une colonne à lit fixe d'adsorbant, avec inversion de flux. Les résultats de simulation du réacteur adsorbeur à inversion de flux pour retenir et recycler les catalyseurs moléculaires ont montré l'intensification du procédé que peut offrir cette technologie en se référant à un réacteur continu conventionnel (réacteur tubulaire monophasique). Il a été montré aussi qu'il n'est pas possible d'atteindre un régime permanent, sans appoint et rajout du catalyseur pour compenser les pertes, dues aux phénomènes physiques indissociables au réacteur. Par la suite, un dispositif expérimental a été construit pour vérifier et valider les résultats de simulations ainsi obtenus, et aussi pour démonter, à l'échelle pilote, la faisabilité de la technologie d'inversion de flux avec adsorption pour séparer l'adsorbé et le retenir à l'intérieur de la colonne. Et similairement au réacteur à inversion de flux pour le recyclage et la réutilisation de la chaleur, le réacteur adsorbeur à inversion de flux pour séparer et recycler le catalyseur, peut lui aussi, avoir un comportement asymptotique sous certaines conditions opératoires, et s'approcher du fonctionnement du réacteur adsorbeur à contre-courant. Par la modélisation et le calcul numérique, il a été établi le domaine des conditions opératoires dans lesquelles, les réacteurs adsorbeurs à inversion de flux et à contre-courant sont équivalents. Le modèle asymptotique à contre-courant permet de calculer et de pré-dimensionner plus rapidement le réacteur à inversion de flux / The reverse flow reactor for heat trapping is an efficient technology that integrates the chemical reaction and the recovery of the heat of the reaction. This technology was widely commercialized and applied in industry because of the reactor productivity enhancement and the process intensification it offers. By heat-matter analogy, we wanted, in this thesis, to evaluate the reverse flow technique and the combination of the chemical reaction with the trapping and the recycling of the catalyst (matter) in one single multi-functional adsorber reactor. The metathesis of olefins that uses molecular catalysts -which are imperfectly immobilized and heterogeneized on the solid support- can be performed in the reverse flow adsorber reactor that claims to separate, recycle and trap the catalyst. The targeted reaction is the self-metathesis of methyl oleate. Thus, a kinetic model of the reaction was developed using a micro-kinetic approach. The obtained kinetic model was fitted to the experiences to get the kinetic parameters values. Then, the kinetic model can be integrated in the reverse flow adsorber reactor model to predict the conversion and the outlet methyl oleate concentration. The reverse flow reactor adsorber was evaluated and studied (by modeling and theoretical study) to have a better understanding of its behavior, and of the operating parameters influence on the process (catalyst leaching, conversion, productivity, etc.). A single fixed bed adsorption column is proposed as a design for the reverse flow adsorber reactor. The simulation results show the process intensification that offers the reverse flow adsorber reactor for catalyst trapping in comparison with a conventional continuous reactor (continuous flow tubular reactor). They also show that it is not possible to reach a stable operation and a permanent regime without catalyst makeup that compensate the leaching. Then, an experimental setup was built to verify, to validate the simulations results, and to demonstrate, at the pilot scale, the feasibility of the reverse flow technology to separate and to trap the adsorbate inside the adsorber. And similarly to the reverse flow reactor for heat trapping, the reverse flow adsorber reactor for catalyst trapping and separation can have an asymptotic behavior under certain operating conditions, and approaches the operation of a counter current adsorber reactor. By modeling and numerical calculation, it has been determined the operating conditions, at which, the reverse flow and the counter current adsorber reactors are equivalents. The counter current asymptotic model allow a rapid reverse flow reactor computing and pre-design

La fonctionnalisation sélective de BINOL en position 6 ou 6 et 6' par des groupements 3 - (diméthylamino)prop-1-yn-1-yl est décrite. Cette méthode constitue une stratégie prometteuse pour le développement de nouveaux ligands recyclables. Les complexes de La et Yb correspondants ont été testés dans la réaction d’époxydation des cétones α, β-insaturées. Les complexes d’ytterbium sont les plus efficaces, fournissant les époxydes chiraux attendus avec 90 ou 93% d’excès énantiomérique en conditions homogène et hétérogène, respectivement.Dans le cadre de nos études, nous avons également évalué de nouveaux catalyseurs comportant un ion de manganèse penta-coordinnée [LMn(III)OH]ClO4 et [LMnCl](MnCl4)0,5. Ces complexes ont été testés dans la réaction d’époxydation des oléfines terminales utilisant H2O2/NaHCO3 et PhIO comme oxydant. Il s'avère que le complexe [LMn(III)OH]ClO4 est le catalyseur le plus efficace de la série. Une autre approche également été envisagée : oxyder une molécule d’eau présente dans la sphère de coordination du métal par le Cerium Ammonium Nitrate (CAN) et utiliser l’espèce oxydante ainsi générée pour oxyder des substrats. Nos études ont montré que cette stratégie était possible et permettait d’oxyder des substrats organiques. / The selective functionalization of BINOL in position 6 or 6 and 6’ with 3-(dimethylamino)prop-1-yn-1yl is described, and it constitutes a promising strategy for the development of a recyclable ligands. The corresponding La and Yb complexes were evaluated towards the epoxidation of α,β-unsaturated ketones. The Yb-complexes displayed an efficient activity, affording the expected chiral epoxides in up to 90 or 93% ee in homogeneous and heterogenous catalysis, respectively.As part of our studies, we also evaluated new catalysts with a penta-coordinated manganese ion [LMn(III)OH]ClO4 and [LMnCl](MnCl4)0.5. These complexes were tested in the epoxidation reaction of terminal olefins using H2O2/NaHCO3 and PhIO as an oxidant. It turns out that the complex [LMn (III) OH] ClO4 is the most efficient catalyst of the series. Another approach was also considered: oxidize a molecule of water present in the coordination sphere of the metal by Cerium Ammonium Nitrate (CAN) and use the generated oxidizing species to oxidize substrates. Our studies have shown that this strategy was feasible and allowed to oxidize organic substrates.

No description available.

Lower C2–C4 olefins are important commodity chemicals usually produced by steam cracking of naphtha or fluid catalytic cracking of vacuum gas oil. The Fischer–Tropsch synthesis of lower olefins (FTO) with iron-based catalysts uses synthesis gas as an alternative feedstock. Nanostructured carbon materials are widely applied as supports for the iron nanoparticles due to their weak interaction with the metal species, facilitating the formation of catalytically active iron carbide. Numerous synthetic approaches towards carbon-supported FTO catalysts with various structures and properties have been published in recent years but structure-performance relationships remain poorly understood. We apply ordered mesoporous carbon (CMK-3) as a support material with well-defined pore structure to investigate the relationships between calcination/activation conditions and catalytic properties. After loading of iron and sodium/sulfur as the promoters, the structures and properties of the FTO catalysts are varied by using different calcination (300–1000 °C) and activation (350 or 450 °C) temperatures followed by FTO testing at 1 bar, 350 °C, H2/CO = 1. Carbothermal reduction of iron oxides by the support material occurs at calcination temperatures of 800 or 1000 °C, leading to a higher ratio of catalytically active iron(carbide) species but the catalytic activity remains low due to particle growth and blocking of the catalytically active sites with dense graphite layers. For the samples calcined at 300 and 500 °C, the formation of non-blocked iron carbide can be enhanced by activation at higher temperatures, leading to higher catalytic activity. Olefin selectivities of ∼60%C in the formed hydrocarbons with methane of ∼10%C are achieved for all catalysts under FTO conditions at low CO conversion. The influence of the calcination temperature is further investigated under industrially relevant FTO conditions. Promoted CMK-3-supported catalysts obtained at low calcination temperatures of 300–500 °C show stable operation for 140 h of time on stream at 10 bar, 340 °C, H2/CO = 2.

The synthesis of a rigid 4,5-bis(triphenylphosphinimino)-2,7-di-tert-butyl-9,9-dimethylxanthene (Ph3PN)2XT (1) ligand is outlined, along with a modified synthesis for previously reported 1,8-bis(triphenylphosphinimino)naphthalene (Ph3PN)2NAP (3). Reaction of neutral (Ph3PN)2XT with [Y(CH2SiMe3)3(THF)2] resulted in double cyclometallation, yielding the base-free monoalkyl complex, [({Ph2(C6H4)PN}2XT)Y(CH2SiMe3)] (2). Layering a concentrated THF solution of 2 with hexanes at −28 °C afforded THF-coordinated [({Ph2(C6H4)PN}2XT) Y(CH2SiMe3)(THF)]·2THF (2-THF·2THF), with a distorted pentagonal bipyramidal geometry and approximately meridional coordination of the pentadentate {Ph2(C6H4)PN}2XT dianion. Similarly, (Ph3PN)2NAP reacted with [Y(CH2SiMe3)3(THF)2] to afford a THF-coordinated monoalkyl complex, [{(Ph2(C6H4)PN)2NAP}Y(CH2SiMe3)(THF)] (4-THF). Layering a DME solution of 4-THF with hexanes at −28 °C afforded X-ray quality crystals of [{(Ph2(C6H4)PN)2NAP}Y(CH2SiMe3)(κ2-DME)]·hexane (4-DME·hexane), with a highly distorted pentagonal bipyramidal geometry and a facial coordination mode of the tetradentate {Ph2(C6H4)PN}2NAP dianion The synthesis of a rigid 4,5-bis(1,3-diisopropylimidazol-2-imine)-2,7,9,9-tetramethylacridan H(AII2) ligand (5) was achieved via a Buchwald-Hartwig cross-coupling reaction. Reaction of the proligand H(AII2) with [M(CH2SiMe3)3(THF)2] (M = Y(6), Sc(8)) yielded the base free dialkyl complexes [(AII2)Y(CH2SiMe3)2] (6) and [(AII2)Sc(CH2SiMe3)2] (8). The reaction of 6 with one equivalent of [CPh3][B(C6F5)4] yielded [(AII2)Y(CH2SiMe3)][B(C6F5)4] (7) in-situ. Complex 7 proved to be a potent intramolecular hydroamination catalyst for a variety of aminoalkane substrates. The attempted synthesis of 4,5-bis(1,3-diisopropylimidazol-2-imine)-2,7-di-tert-butyl-9,9-dimethylxanthene (XII2) via the Staudinger reaction resulted in the isolation of the triazene intermediate 4,5-bis(1,3-diisopropylimidazol-2-yliedene{triazene})-2,7-di-tert-butyl-9,9-dimethylxanthene XIA2 (9). Reaction of XIA2 with one equivalent of [Y(CH2SiMe3)3(THF)2] led to the isolation of [(XIA2)Y(CH2SiMe3)3] (10). Synthesis of XII2 (11) was achieved via a Buchwald-Hartwig cross-coupling reaction. Reaction of XII2 with one equivalent of YCl3(THF)3.5 resulted in the isolation of [(XII2)YCl3] (12). In contrast, the reaction of XII2 with one equivalent of [Y(CH2SiMe3)3(THF)2] led to several unidentified products. Reaction of XII2 with 1 equivalent of [H(Et2O)2][B(C6F5)4] led to the isolation of the precursor [H(XII)2][B(C6F5)4] (13). The reaction of 13 with 1.1 equivalents of [M(CH2SiMe3)3(THF)2] (M = {Y(14), Sc(15)} led to the isolation of the monocationic [(XII)2M(CH2SiMe3)2][B(C6F5)4] complexes. The reaction of [(XII)2Sc(CH2SiMe3)2][B(C6F5)4] with 1.1 equivalents of B(C6F5)3 led to the abstraction of a methyl anion from the silicon center, with concomitant migration of the remaining alkyl group to the positively charged silicon, forming a new CH2SiMe2CH2SiMe3 alkyl group. This process is accompanied by MeB(C6F5)3 anion formation, forming a contact ion pair to afford the dicationic species [(XII)2Sc(CH2SiMe3)][MeB(C6F5)3][B(C6F5)4] 16. In contrast, the reaction of 15 with 1.3 equivalents of [CPh3][B(C6F5)4] in the presence of 5 equivalents of toluene resulted in the synthesis of [(XII)2Sc(CH2SiMe3)(ɳx-toluene)][B(C6F5)4]2 17 in-situ. Complex 17 is a highly potent ethylene polymerization catalyst with an activity of 868 kg/mol·atm·h. The reaction of 15 with [HNMe2Ph][B(C6F5)4] led to the cyclometallation of the resulting NMe2Ph byproduct to yield [(XII2)Sc(C6H4NMe2)][B(C6F5)4]2 (18) in-situ. The synthesis of a rigid, asymmetric 4-(1,3-diisopropylimidazol-2-imine)-5-(2,6-diisopropylanilido)- 2,7-di-tert-butyl-9,9-dimethylxanthene XAI (19) ligand was achieved by a two step Buchwald-Hartwig cross-coupling reaction with initial cross coupling of 1,3-diisopropylimidazol-2-imine followed by the cross-coupling of 2,6-diisoproylaniline. The reaction of XAI with 1.1 equivalents of [Y(CH2SiMe3)3(THF)2] yielded [(XAI)Y(CH2SiMe3)2] (20). Subsequent reaction of [(XAI)Y(CH2SiMe3)2] with 1 equivalent of [CPh3][B(C6F5)4] in the presence of 10 equivalents of toluene resulted in the synthesis of the toluene coordinated [(XAI)Y(CH2SiMe3)(ɳx-toluene)][B(C6F5)4] (21) complex. Similar to 7, complex 21 was highly active for intramolecular hydroamination of various substrates. / Dissertation / Doctor of Philosophy (PhD) / Cationic group 3 alkyl complexes are underreported in comparison to analogous group 4 complexes. The scarcity of these complexes can be attributed to their propensity to engage in undesirable reactions such as ligand redistribution and cyclometallation. To increase the thermal stability of such complexes, design features, such as carefully positioned steric bulk and ligand rigidity are beneficial. Additionally, such ligands must also have considerable donor ability, in order to stabilize inherently electron deficient cationic metal centers. This work details the synthesis of a variety of neutral and monoanionic ligands that incorporate the aforementioned design features, which were utilized in the successful synthesis of a variety of neutral, monocationic and extremely rare dicationic group 3 alkyl complexes. The cationic monoalkyl complex in this work proved to be a highly potent intramolecular hydroamination catalyst. Furthermore, a rare dicationic scandium complex was highly active for ethylene polymerization