The two major topics studied in this dissertation are the gold(I) pyrazolate trimer {[Au(3-R,5-R’)Pz]3} complexes in aqueous chitosan polymer and phosphorescent polymeric nanoparticles based on platinum(II) based complex. The first topic is the synthesis, characterization and optical sensing application of gold(I) pyrazolate trimer complexes within aqueous chitosan polymer. A gold(I) pyrazolate trimer complex, {[Au(3-CH3,5-COOH)Pz]3}, shows high sensitivity and selectivity for silver ions in aqueous media, is discussed for optical sensing and solution-processed organic light emitting diodes (OLEDs) applications. Gold(I) pyrazolate trimer complexes are bright red emissive in polymeric solution and their emission color changes with respect to heavy metal ions, pH and dissolved carbon dioxide. These photophysical properties are very useful for designing the optical sensors. The phosphorescent polymeric nanoparticles are prepared with Pt-POP complex and polyacrylonitrile polymer. These particles show excellent photophysical properties and stable up to >3 years at room temperature. Such nanomaterials have potential applications in biomedical and polymeric OLEDs. The phosphorescent hybrid composites are also prepared with Pt-POP and biocompatible polymers, such as chitosan, poly-l-lysine, BSA, pnipam, and pdadmac. Photoluminescent enhancement of Pt-POP with such polymers is also involved in this study. These hybrid composites are promising materials for biomedical applications such as protein labeling and bioimaging.

No description available.

This work focuses on the design and synthesis of Au(I) and Ag(I) complexes from ligand systems that aim to combine both N-heterocyclic carbene (NHC) and phosphine ligand types. A number of synthetic approaches towards both the ligands and the prepared metal complexes have been developed, with a concerted effort on achieving the desired Au(I) or Ag(I) complexes with minimal reaction steps and synthetic style. The thesis body is divided into two main sections. The first section addresses the preparation of suitable ligand precursors of potential Au(I) and Ag(I) complexes in the form of halo- and phosphino-functionalised imidazolium salts. Several series of haloalkylimidazolium salts were prepared that encompass a range of halogens (Cl, Br, I), alkyl substituents (Me, i-Pr, t-Bu, n-Bu), differing alkyl linker length (n = 0-3), and a variety of organic spacers employed to bridge multi-imidazolium moieties. Novel bidentate and multidentate phosphinoalkylimidazolium salts were synthesised from the various haloalkylimidazolium salts, via the substitution of a halide with nucleophilic diphenylphosphide. A new approach towards rare methylene bridged phosphinomethylimidazolium salts was achieved from the reactions of halomethylimidazolium salts with diphenylphosphine. The second section investigates the preparation of Au(I) and Ag(I) complexes from the halo- and phosphino-functionalised imidazolium salts. A series of dicationic 10, 12, and 14-membered metallacyclic Ag(I) complexes were prepared from the bidentate phosphinoalkylimidazolium salts. The dinuclear Ag(I) metallacycles combine two phosphino-functionalised NHC ligands that are bridged by two coordinated Ag(I) ions in an exclusively head-to-head arrangement. A dinuclear Ag(I) metallacycle was investigated for transmetallation potential to a Au(I) complex and found to selectively transmetallate at the Ag(I) coordinated to the NHC ligands to form a bimetallic metallacycle. Unexpected phosphine oxidation of a 10-membered dinuclear Ag(I) metallacycle resulted in complex disproportionation to an isolable and rare silver(I) trimer. Metal-NHC complexes from haloalkylimidazolium salts have not been reported previously, a novel approach to the synthesis of a series of Au(I) complexes from haloalkylimidazolium salts and a respective gold source was developed and is reported herein. Different synthetic approaches towards Au(I) complexes with the phosphinoalkylimidazolium salts explored a variety of ways to generate the NHC from an imidazolium in the presence of the phosphine. A one-pot, high yielding synthesis of a dinuclear Au(I) complex from PPh3 was also devised, with controlled assembly of the complex resulting in a similar head-to-head ligand arrangement to the dinuclear Ag(I) metallacycles. As an aside, a family of mononuclear [Au(R2NHC)2]+ complexes (R = Me, i-Pr, t- Bu, n-Bu, Cy) prepared previously in our research group, was expanded because of the promising antimitochondrial activity shown by [Au(i-Pr2NHC)2]+. Two new [Au(R2NHC)2]+ complexes with simple alkyl chain functionality were prepared with fine-tuned lipophilicity in close proximity to that of [Au(i-Pr2NHC)2]+.

Ce travail de thèse porte sur la chimie organométallique des complexes d'or(I) et sur l'étude de leurs réactivités. Plus particulièrement, le travail présenté ici dans ce manuscrit avait pour objectif d'approfondir nos connaissances sur l'impact des ligands utilisés sur la réactivité de l'or vis-à-vis (i) de l'addition oxydante intermoléculaire et (ii) la possibilité de stabiliser des intermédiaires d'or(I) hautement réactifs. Dans la première partie de ce manuscrit, l'addition oxydante intermoléculaire des halogénures d'aryle (iodure et bromure) à des complexes moléculaires d'or(I) a été étudiée en détails. Nous avons pu montrer que cette étape élémentaire de la chimie organométallique, considéré comme impossible avec l'or, était en fait un processus favorable lorsqu'un ligand adéquat est employé, et deux stratégies différentes ont été élaborées. La première consiste à utiliser un ligand bis-phosphine bidenté qui impose une géométrie coudée autour de l'or, tandis que la deuxième stratégie implique l'utilisation d'un ligand hémi-labile bidenté avec des groupements donneurs doux et dur. Les deux stratégies ont été fructueuses, et les complexes d'or(III) issus des réactions d'addition oxydante ont été caractérisés spectroscopiquement et structuralement. Dans la deuxième partie, ayant à notre disposition deux complexes d'or(I) capable d'effectuer l'addition oxydante, nous voulions aller au-delà de cette étape élémentaire. Dans cet objectif, nous avons construit un nouveau cycle catalytique Au(I)/Au(III) impliquant une séquence d'addition oxydante Csp2-X, de Csp2-H auration et d'élimination réductrice, illustrant le premier exemple d'arylation directe d'arènes avec des halogénures d'aryle catalysée à l'or. Enfin, dans la dernière partie, nous avons tenté de stabiliser et de caractériser des intermédiaires d'or(I) très instables, comme le a-oxo carbène d'or(I). Cette espèce hautement électrophile est proposée comme un intermédiaire clés dans des nombreuses transformations catalytiques, mais n'a jamais été isolé ou caractérisé (en solution ou à l'état solide). L'utilisation d'un ligand bis-phosphine bidenté nous a permis de caractériser spectroscopiquement et structuralement le carbène a-oxo d'or(I) pour la première fois. Nous avons ensuite étudié sa réactivité vis-à-vis des réactions d'insertion et de cyclopropanation. / The present work is an organometallic study concerning the chemistry of gold(I) complexes and their reactivity. Of particular interest was to gain further knowledge on the impact of the ligands employed on the reactivity of gold towards (i) the intermolecular oxidative addition of aryl halides and (ii) the possibility of stabilizing high reactive gold(I) intermediates. In the first part of the manuscript, the intermolecular oxidative addition of aryl halides (iodide and bromide) with molecular gold(I) complexes was investigated in detail. We showed that this organometallic elementary step, usually considered to be impossible for gold, is actually a favorable process when an adequate ligand is employed and two different strategies have been elaborated. The first one consists in the use of a bis-phosphine bidentate ligand that forces a bent geometry around gold, whereas the second strategy implicates the use of a hemi-labile bidentate ligand bearing a soft and a hard donor group. Both strategies were found fruitful, and the gold(III) complexes stemming from oxidative addition reactions were characterized by spectroscopic and structural means. In the second part, having in hands two gold(I) complexes that undergo the oxidative addition reaction, we wanted to go beyond this elementary step. In that objective, we constructed a new Au(I)/Au(III) catalytic cycle involving a sequence of Csp2-X oxidative addition, Csp2-H auration and reductive elimination, allowing the first example of gold-catalyzed direct arylation of arenes with aryl halides. Finally, in the last part, we attempted to stabilize and characterize high reactive gold(I) intermediates, like the a-oxo gold(I) carbenes. This electrophilic species is proposed in many catalytic transformations as key intermediates, but has never been isolated or characterized (in solution or in solid state). The use of a bidentate diphosphine ligand allowed the characterization of the a-oxo gold(I) carbene for the first time by means of multinuclear NMR spectroscopy, X-ray diffraction analysis and high resolution mass spectroscopy (ESI+). We then investigated the reactivity of the a-oxo gold(I) carbene towards insertion and cyclopropanation reactions. Interestingly, the reactivity of the generated gold(I) carbenes can be modulated depending on the electronic properties of the aryl ethyl diazoacetate used.

Le premier projet de ce travail de doctorat a consisté à étudier l’activité catalytique de complexes à base de gallium(I), pour continuer à rechercher des alternatives aux catalyseurs à base de métaux nobles, plus communs, mais réputés coûteux et/ou toxiques. Le savoir-faire de l’équipe en catalyse par des complexes de gallium(III) a pu être réinvesti dans l’étude de ce bas degré d’oxydation du gallium, rarement étudié dans la littérature scientifique, dans l’espoir de détecter des réactivités et/ou sélectivités différentes d’avec des complexes de gallium(III). Ainsi, le complexe cationique bien défini de gallium(I) [Ga(PhF)2][Al(OC(CF3)3)4] a été employé dans une large gamme de réactions dans lesquelles les catalyseurs à base de gallium(III) avaient déjà fait leurs preuves, telles que l’hydroarylation d’arénynes, la réaction de Friedel-Crafts ou encore l’hydrogénation d’alcènes par transfert, pour laquelle une réactivité supérieure à celle des complexes usuellement utilisés au sein de l’équipe a été observée. Un analogue à base d’indium(I), [In(PhF)2][Al(OC(CF3)3)4], a également été étudié dans ces réactions, sans succès. En revanche, il s’est avéré efficace dans le cadre de réactions d’hydroamination d’aminoalcènes.En parallèle a été conduit un projet basé sur l’étude en tant qu’abstracteurs d’halogénures de complexes de divers métaux (argent, lithium, potassium, thallium(I)) comportant l’anion perfluoré, très volumineux et très faiblement coordinant [Al(OC(CF3)3)4]-. Dans le cadre de l’activation de pré-catalyseurs à base d’or(I), de gallium(III) ou d’indium(III) par abstraction d’halogénures, les sels d’argent sont les plus communément employés dans la littérature. Cependant, ces sels d’argents ne sont pas innocents en termes de réactivité. Par ailleurs, si les cations métalliques des sels employés en abstraction d’halogénures font l’objet d’un nombre raisonnable d’études dans la littérature, ce n’est pas autant le cas des anions qui leur sont associés : notre étude s’oriente selon ces deux problématiques. Il s’est avéré que les propriétés très faiblement coordinantes de l’anion [Al(OC(CF3)3)4]- ont mené à des réactivités et sélectivités différentes de celles obtenues avec l’emploi de sels plus usuels, AgSbF6 plus particulièrement, dans le cadre de réaction classiquement catalysées par l’or(I) ou le gallium(III) et déjà étudiées dans le premier projet de ce travail de thèse. Les complexes à base de gallium(I) et d’indium(I) impliqués dans le premier projet ont également été, succinctement, étudiés dans ce projet parallèle. / In the main project of this thesis work, the catalytic activity of gallium(I)-based complexes was explored. The aim was to keep on looking for alternatives to noble metals-based, more common catalysts, which have a reputation for being expensive and/or toxic. The know-how developed in the team on gallium(III)-based catalysis was reinvested into the study of this low oxidation degree of gallium, only scarcely studied in the literature. It was hoped to then detect different reactivity and/or selectivity than with gallium(III) complexes. Thus, the well-defined, cationic, gallium(I)-based complex [Ga(PhF)2][Al(OC(CF3)3)4] was used in a large array of reactions that were already successfully studied with gallium(III)-based catalysts, such as the hydroarylation of arenynes, the Friedel-Crafts reaction or the transfer hydrogenation of alkenes. In this later reaction in particular, the observed reactivity was superior to that achieved with the catalysts more commonly used in the team. An indium(I)-based analogue, [In(PhF)2][Al(OC(CF3)3)4], was also tested in these reactions, without any success. However, it was actually efficient in the context of aminoalkenes hydroamination reactions.The side-project of this work consisted in the study as halide abstractors of complexes, based on diverse metals (silver, lithium, potassium, thallium(I)) and containing the perfluorinated, very bulky and very weakly coordinating anion (WCA) [Al(OC(CF3)3)4]-. In the frame of the activation of gold(I), gallium(III) or even indium(III)-based pre-catalysts by halide abstraction, silver salts are the most frequently used. However, these silver salts are not non-innocent in terms of reactivity. Besides, if the cationic metal of the salts used in halide abstraction are the subject of a reasonable amount of studies in the literature, it is not the case of their anionic counterparts: we planned to address these two problematics with this project. It appeared that the very weakly coordinating properties of the anion [Al(OC(CF3)3)4]- in the context of the previously referred to reactions classically catalyzed by gold(I) or gallium(III)-based complexes led to different reactivity and selectivity than those achieved with the usual salts and in particular AgSbF6. The gallium(I) and indium(I)-based complexes involved into the main project were also briefly studied in this side-project.

La catalyse organométallique est l’un des outils les plus puissants de la synthèse chimique, car elle permet de réaliser des transformations sélectives et spécifiques selon le catalyseur employé. Dans ce contexte, les sels et complexes d’or ont émergé il y a une quinzaine d’années et se sont révélés très utiles et attractifs pour la synthèse organique, faisant preuve de propriétés particulières de type acide de Lewis à la fois π (alcyno- alcènophilie) et σ (oxo- azaphile). L’objectif initial de cette thèse a été d'approfondir l’étude de la réactivité de l’or au travers la mise au point de nouvelles réactions catalysées par l’or(I/III). Si la majorité des réactions développées en catalyse à l’or concerne des processus de type π, nous avons dans un premier temps, souhaité évaluer son potentiel dans une réaction qui repose sur une activation purement σ, la cyclisation de Nazarov. Cette réaction a ensuite été étendue à un processus de type cascade, combinant activations π et σ. De plus, la formation d’un sous-produit inattendu au cours de cette étude a orienté nos recherches vers un nouveau processus catalytique, le réarrangement de γ–acyloxy alcynylcétones en furanes. Par la suite, nous nous sommes aussi intéressés au potentiel de l’or dans les réactions asymétriques, ce qui a conduit au développement d’un nouveau type de complexes d’or chiraux basés sur des ligands de type NHC-oxazoline. Enfin, nous nous sommes proposés d’utiliser la spectroscopie RMN J-résolue hétéronucléaire (une méthode simple mais peu exploitée), pour répondre à des problèmes d’attribution structurale. / Organometallic catalysis is one of the most powerful tools in chemical synthesis, because, depending on the catalyst, it allows for selective and specific transformations. Thus, the reactivity of gold salts and complexes was revamped around fifteen years ago. Nowadays, they are considered as powerful and very attractive for organic synthesis, showing both π (alcyno- alcènophilie) and σ (oxo- azaphile) Lewis acid properties.The first objective of this thesis was to study the reactivity of gold catalysts by the development of new reactions catalyzed by gold(I/III). If most of the developed reactions in gold catalysis is related to π activation, we proved its potential in a reaction dealing with σ activation, the Nazarov cyclization. This reaction was then extended to a cascade process, combining both π and σ Lewis acidities. Moreover, the obtainment of an unexpected by-product during the study directed our research towards a new gold catalytic reaction, the formation of furans from γ-acyloxyalkynyl ketones. Subsequently, we were also interested in the potential of gold in asymmetric reactions, which led to the development of new chiral gold complexs, based on NHC-oxazoline type ligands. Finally, we proposed to use the heteronuclear J-resolved NMR spectroscopy (a simple but scarce method), to answer some structural assignment problems.

Ce travail est axé vers la compréhension détaillée des propriétés de luminescence de composés de certains métaux lourds. La première partie de ce mémoire décrit la caractérisation spectroscopique d'un radical de type nitronyle nitroxyde, 2-(2-pyridinyl)-4,4,5,5-tétraméthyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxyde, abrégé (NIT2-Py), et de ses complexes avec les cations Tb(III), [Tb(hfac)3NIT2-Py], et Y(III), [Y(hfac)3NIT2-Py]. La variation de la température affecte les spectres de luminescence qui montrent de la structure vibronique résolue. Les maxima de ces transitions vibroniques se rapprochent au fur et à mesure que la température augmente. Ces variations des maxima en fonction de la température ne correspondent pas à des variations de fréquences vibrationnelles et sont de l'ordre de 200 cm-1 entre 80 K et 240 K. La variation de la température n'a pas d'influence significative sur la structure moléculaire, comme atteste la variation mineure des maxima des spectres Raman entre 80 K et 300 K. La comparaison des spectres expérimentaux à des spectres calculés montre que ces variations peuvent être reproduites par l'utilisation d'une combinaison de fréquences vibrationnelles. Le paramètre dont la variation est très significative est la résolution du spectre de luminescence, représentée par la largeur à mi-hauteur des transitions vibroniques qui forment le spectre de luminescence. La deuxième partie de ce mémoire décrit les propriétés de luminescence d'une série de complexes d’or(I). Elles sont comparées aux changements structuraux à pression et température variable. Les interactions aurophiles ont une grande influence sur la luminescence. La variation de la température et de la pression est une approche efficace pour varier la luminescence. Les effets observés dans les spectres d'émission de ces complexes dépendent des changements de structure induits par variation de la température et de la pression. Ces petites variations structurales mènent à des changements importants, à titre d'exemple à un déplacement du maximum de la bande de luminescence de 60 cm-1/ kbar vers les faibles énergies pour un des complexes de l'or(I) étudiés au cours de ce projet. / The overall goal of this work is to contribute to the understanding of luminescence properties of transition metal compounds. The first part of this thesis describes the spectroscopic characterization of a pyridine-substituted nitronyl nitroxyde radical 2-(2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-3-oxide-1-oxyl abbreviated (NIT2-Py) and its complexes with Tb(III) and Y(III), [Tb(hfac)3NIT2-Py] and [Y(hfac)3NIT2-Py], respectively. Their luminescence spectrum show resolved vibronic structure and variations with temperature The energy difference between vibronic luminescence maxima decreases with increasing temperature. This decrease is on the order of 200 cm-1 between 80 K and 240 K and is not due to decreasing Raman frequencies. The variations of temperature do not have a significant influence on the molecular structures, as illustrated by the very small variation of Raman maxima between 80 K and 300 K. Luminescence spectra were calculated using the time dependent theory of spectroscopy. Calculated luminescence spectra show that the variations with temperature are reproduced by using specific combinations of experimental frequencies and by adjusting the width of the vibronic transitions, determining the resolution of the luminescence spectrum. The second part of the thesis describes the luminescence spectroscopic properties of a series of trimetallic gold(I) complexes at variable temperature and pressure. Aurophilic interactions are very important for these compounds and influence the luminescence spectra. The spectroscopic features are compared to structural changes at variable temperature and pressure. Even small changes in structure lead to significant changes in luminescence, for example a shift of the maximum of the luminescence band by 60 cm-1/ kbar to lower energy for one of the gold(I) complexes studied.

Ce travail est axé vers la compréhension détaillée des propriétés de luminescence de composés de certains métaux lourds. La première partie de ce mémoire décrit la caractérisation spectroscopique d'un radical de type nitronyle nitroxyde, 2-(2-pyridinyl)-4,4,5,5-tétraméthyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxyde, abrégé (NIT2-Py), et de ses complexes avec les cations Tb(III), [Tb(hfac)3NIT2-Py], et Y(III), [Y(hfac)3NIT2-Py]. La variation de la température affecte les spectres de luminescence qui montrent de la structure vibronique résolue. Les maxima de ces transitions vibroniques se rapprochent au fur et à mesure que la température augmente. Ces variations des maxima en fonction de la température ne correspondent pas à des variations de fréquences vibrationnelles et sont de l'ordre de 200 cm-1 entre 80 K et 240 K. La variation de la température n'a pas d'influence significative sur la structure moléculaire, comme atteste la variation mineure des maxima des spectres Raman entre 80 K et 300 K. La comparaison des spectres expérimentaux à des spectres calculés montre que ces variations peuvent être reproduites par l'utilisation d'une combinaison de fréquences vibrationnelles. Le paramètre dont la variation est très significative est la résolution du spectre de luminescence, représentée par la largeur à mi-hauteur des transitions vibroniques qui forment le spectre de luminescence. La deuxième partie de ce mémoire décrit les propriétés de luminescence d'une série de complexes d’or(I). Elles sont comparées aux changements structuraux à pression et température variable. Les interactions aurophiles ont une grande influence sur la luminescence. La variation de la température et de la pression est une approche efficace pour varier la luminescence. Les effets observés dans les spectres d'émission de ces complexes dépendent des changements de structure induits par variation de la température et de la pression. Ces petites variations structurales mènent à des changements importants, à titre d'exemple à un déplacement du maximum de la bande de luminescence de 60 cm-1/ kbar vers les faibles énergies pour un des complexes de l'or(I) étudiés au cours de ce projet. / The overall goal of this work is to contribute to the understanding of luminescence properties of transition metal compounds. The first part of this thesis describes the spectroscopic characterization of a pyridine-substituted nitronyl nitroxyde radical 2-(2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-3-oxide-1-oxyl abbreviated (NIT2-Py) and its complexes with Tb(III) and Y(III), [Tb(hfac)3NIT2-Py] and [Y(hfac)3NIT2-Py], respectively. Their luminescence spectrum show resolved vibronic structure and variations with temperature The energy difference between vibronic luminescence maxima decreases with increasing temperature. This decrease is on the order of 200 cm-1 between 80 K and 240 K and is not due to decreasing Raman frequencies. The variations of temperature do not have a significant influence on the molecular structures, as illustrated by the very small variation of Raman maxima between 80 K and 300 K. Luminescence spectra were calculated using the time dependent theory of spectroscopy. Calculated luminescence spectra show that the variations with temperature are reproduced by using specific combinations of experimental frequencies and by adjusting the width of the vibronic transitions, determining the resolution of the luminescence spectrum. The second part of the thesis describes the luminescence spectroscopic properties of a series of trimetallic gold(I) complexes at variable temperature and pressure. Aurophilic interactions are very important for these compounds and influence the luminescence spectra. The spectroscopic features are compared to structural changes at variable temperature and pressure. Even small changes in structure lead to significant changes in luminescence, for example a shift of the maximum of the luminescence band by 60 cm-1/ kbar to lower energy for one of the gold(I) complexes studied.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-04T12:42:14Z No. of bitstreams: 1 angelinamariadealmeida.pdf: 23133254 bytes, checksum: 7560d658fe12ed7f6166fc99ab314157 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-17T13:30:51Z (GMT) No. of bitstreams: 1 angelinamariadealmeida.pdf: 23133254 bytes, checksum: 7560d658fe12ed7f6166fc99ab314157 (MD5) / Made available in DSpace on 2017-05-17T13:30:51Z (GMT). No. of bitstreams: 1 angelinamariadealmeida.pdf: 23133254 bytes, checksum: 7560d658fe12ed7f6166fc99ab314157 (MD5) Previous issue date: 2016-07-29 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Os valores terapêuticos do ouro são conhecidos desde a China antiga e, atualmente, complexos de ouro são empregados no tratamento da artrite reumatóide. Outras propriedades biológicas relativas aos complexos de ouro(I) vêm sendo reportadas na literatura, como atividade antitumoral, antibacteriana, antiviral e antifúngica. A primeira parte dessa tese descreve a síntese de novos complexos lipofílicos de ouro(I) contendo núcleo 1,3,4-oxadiazol-2-tiona ou 1,3-tiazolidina-2-tiona, além de serem constituídos por fosfinas terciárias, como trifenilfosfina ou trietilfosfina. Após caracterização através de métodos espectroscópicos usuais (RMN de 1H, 13C, 31P, IV e EMAR), foram realizadas avaliações biológicas in vitro para todos os complexos de ouro(I) e seus respectivos ligantes orgânicos. Os resultados citotóxicos frente a linhagens tumorais (CT26WT e B16F10) e normais (BHK21) indicam acentuada atividade antitumoral devido aos baixos valores de IC50 quando comparados aos valores obtidos para os ligantes orgânicos e para a Cisplatina. A atividade antibacteriana dos complexos de ouro(I) contra as bactérias Gram-positivas Staphylococcus aureus e Staphylococcus epidermidis também mostrou-se satisfatória, uma vez que os complexos exibem baixos valores de CIM comparados aos resultados obtidos para os ligantes orgânicos e cloranfenicol. O desenvolvimento de metodologias de catálise por metais de transição, em especial o uso de paládio, tem atraído considerável atenção no meio acadêmico e industrial. Assim, a segunda parte do trabalho aborda o desenvolvimento de um método geral de preparação de ésteres ativos via alcoxicarbonilação catalisada por paládio e o acoplamento carbonilativo entre haletos de arila, cianato de potássio, álcoois e monóxido de carbono catalisada por paládio. Em ambos os casos, verifica-se a generalidade dos protocolos devido à diversidade e aos bons rendimentos do escopo obtido a partir de diferentes nucleófilos e haletos aromáticos e heteroaromáticos. / Therapeutic gold values are known since ancient China and gold complexes are currently employed in the treatment of rheumatoid arthritis. Other biological properties relative to the complexes of gold(I) have been reported in the literature, such as antitumor activity, antibacterial, antiviral and antifungal. The first part of this thesis describes the synthesis of novel lipophilic complexes of gold(I) containing core 1,3,4-oxadiazol-2-thione or 1,3-thiazolidine-2-thione, and they are constituted by tertiary phosphines, such as triphenylphosphine or triethylphosphine. After characterization using usual analythical methods (NMR 1H, 13C, 31P, IR and HRMS) the biological evaluations were performed in vitro for all complexes of gold(I) and their organic ligands. The cytotoxic results against tumor cells (CT26WT and B16F10) and normal cells (BHK21) show pronounced antitumor activity due to low IC50 values compared to the values obtained for the corresponding ligands and Cisplatin. The antibacterial activity for the complexes of gold(I) against Gram-positive bacteria Staphylococcus aureus and Staphylococcus epidermidis also proved to be satisfactory, since the complexes exhibit low MIC values compared to the results obtained for the ligands and chloramphenicol. The development of catalytic methodologies by transition metals, in particular the use of palladium, has attracted considerable attention in the academia and industry. Thus, the second chapter covers the development of a general method for preparation of active esters via palladium catalyzed alkoxycarbonilation and carbonilative coupling of aryl halides, potassium cyanate, alcohols and carbon monoxide. In both cases the generality of the protocols is confirmed by the diversity and good yields obtained to the scope from different nucleophiles and aromatic and heteroaromatic halides.

This work deals with the determination of the single crystal structure analysis of four triazenido complexes including gold(I), copper(I), silver(I), and the crystal structure of a free triazene molecule. Crystal data and refinement indices of 1-(4-carboxyphenyl)-3-(4- acetylamidophenyl)triazene (1) are: monoclinic system, space group P21/n, cell parameters a = 7.772(1), b = 9.7365(2), c = 19.55(3) Å, β = 93.435(1)º, Z = 4, R1 = 0.0394, wR2 = 0.0632. The crystal structure show that the molecule deviates significantly from planarity (r.m.s. 0.342 Å). The molecules of (1) are associated to a bi-dimensional supramolecular array in form of helix chains including classic hydrogen bonding in the [010] crystallographic direction. Crystal data and refinement indices of 1-(4-ethoxycarbonylphenyl)-3-(4-nitrophenyl)triazenide(triphenylphosfine)gold(I) (3) are: triclinic system, space group P(-1), cell parameters a = 9.8837(2), b = 12.6159(2), c = 13.0948(2) Å, α = 79,160(1)°, β = 78,411(1)°, γ = 73,731(1)°, Z = 2, R1 = 0.0271, wR2 = 0.0588. One deprotonated triazenido ligand and one triphenylphosfine molecule built the linear coordination geometry of gold(I). Crystal data and refinement indices of 1-(4-ethoxycarbonylphenyl)-3-(4-nitrophenyl)-bis-(triphenylphosfine)copper(I) (4) are: triclinic system, space group P(-1), cell parameters a = 10.9853(2), b = 14.6006(3), c = 16.0638(3) Å, α = 79.160(1)°, β = 78.411(1)°, γ = 73.731(1)°, Z = 2, R1 = 0.0370, wR2 = 0.0996. One deprotonated triazenido ligand and three neutral triphenylfosfine molecules complete the distorted tetrahedral coordination sphere of copper(I). Crystal data and refinement indices of trans-bis-1-(4-ethoxycarbonylphenyl)-3-(4-nitrophenyl)triazenide-bis-(pyridine)silver(I) (5) are: triclinic system, space group P(-1) with cell parameters a = 9.3123(4), b = 11.1234(5), c = 11.1914(5) Å, α = 71.165(3)°, β = 68.723(3)°, γ= 89.530(3)°, Z = 2, R1 = 0.0383 wR2 = 0.0856. Two deprotonated monodentate triazenido ligands and two pyridine molecules in trans position relative to each other in a eight-membered Ag2N6 fragment, perform the Tcoordination geometry of each silver(I) ion. Crystal data and refinement indices of Catena-[bis(μ2-ciano)-bis(triphenilphosfine)-di-silver(I)] (6) are: monoclinic system, space group P21/n with cell parameters a = 9.3174(4), b = 22.931(1), c = 16.1513(8) Å, β = 99.759(3)°, Z = 4, R1 = 0.0526, wR2 = 0.1337. Two neutral triphenilfosfine molecules and two cyanide ligands support the distorted tetrahedral coordination geometry of the silver(I) ion in a open catenated coordination polymer. / Este trabalho apresenta a determinação da estrutura cristalina e molecular de quatro complexos sendo um com ouro(I), outro com cobre(I) e dois complexos de prata(I), adicionalmente incluindo a estrutura cristalina e molecular de um composto triazeno livre O composto 1-(4-carboxifenil)-3-(4-acetilamidofenil)triazeno(1) cristaliza no sistema monoclínico, grupo espacial P21/n, com parâmetros de cela a = 7,7723(10) Å, b = 9,7365(2) Å, c = 19,355(3) Å, β = 93,4350(10)º, V = 1462,09(4) Å3, Z = 4, R1 = 0,0394, wR2 = 0,1093. A estrutura cristalina do pró-ligante (1) revela que a molécula não é planar (r.s.m. 0,3148Å) e que, as moléculas unem-se por ligações de hidrogênio na direção cristalográfica [010]. As ligações de hidrogênio são do tipo clássicas N H O, O H O e O H N, que se relacionam por operações de simetria formando um arranjo bidimensional. O composto (3) cristaliza do sistema triclínico, grupo espacial P(-1) com parâmetros de cela a = 9,8837(2) Å, b = 12,6159(2) Å, c = 13,0948(2) Å; α= 79,1600(10)°, β= 78,4110(10)°, γ = 73,7310(10)°; V = 1520,32(5) Å3 ; Z = 2. O refinamento desta estrutura conduziu aos índices de discordância R1 = 0,0271, wR2 = 0,0588. A esfera de coordenação do íon ouro(I) é formada por um ligante triazeno desprotonado e uma moléculas de trifenilfosfina. O composto (4) cristaliza no sistema triclínico, grupo espacial P(-1) com parâmetros de cela a = 10,9853(2) Å, b = 14,6006(3) Å , c = 16,0638(3) Å, α = 97,1150(10)°, β = 102,9530(10)°, γ = 110,8030(10)°; V = 2287,95(8) Å3 ; Z = 2. O refinamento desta estrutura conduziu aos índices de discordância R1 = 0,0370, wR2 = 0,0996. A esfera de coordenação do íon cobre(I) é formada por um ligante triazeno desprotonado e duas moléculas de trifenilfosfina. O composto (5) binuclear cristaliza no sistema triclínico, grupo espacial P (-1) com parâmetros de cela a = 9,3123(4) Å, b = 11,1234(5) Å, c = 11,1914(5) Å, α = 71,165(3)°, β = 68,723(3)°, γ = 89,530(3)°; V = 1014,56(8) Å3 ; Z = 2. O refinamento desta estrutura demonstrou os índices de discordância R1 = 0,0383, wR2 = 0,0856. A esfera de coordenação do íon prata(I) é formada por dois ligantes triazenos desprotonados e duas moléculas de piridina. O composto (6) polímero cristaliza no sistema monoclínico, grupo espacial P21/n com parâmetros de cela a = 9,3174(4) Å, b = 22,9314(14) Å, c = 16,1513(8) Å, β = 99,759 (3)°; V = 3401,0(3) Å3 ; Z = 4. O refinamento desta estrutura atingiu os índices de discordância R1 = 0,0526, wR2 = 0,1337. A esfera de coordenação do íon prata(I) é formada por dois ligantes trifenilfosfina e dois cianetos.