Foi investigada a reação de inserção de isonitrilas (fenil-, o-toluil-, a-metilbenzil-, benzil- e terc-butil-) na ligação M-C dos seguintes complexos N-paladociclos: o bis (8-etilquinoleína-C,N) di (J..l-CI) dipaládio 11 e os seus derivados obtidos por substituição do grupo etila por outros grupos que contenham ligação M-C alquílica e, o bis (N,N-dimetilbenzilamina-C,N) di (J..l-Cl) dipaládio fi, que contém ligação M-C arílica. Enquanto que as reações de inserção de isonitrilas na ligação Pd-C ocorrem facilmente com o último complexo, produtos de inserção com os complexos derivados de 8-etilquinoleína só são observados quando um grande excesso de fenilisonitrila é empregado, e assim mesmo, somente produtos derivados de polimerização da isonitrila foram caracterizados. / We investigated the insertion reaction of some isocyanides (phenyl-, o-tolyl-, amethylbenzyl-, benzyl- and terc-butyl-) into M-C bond of two cyclopalladated complexes: the bis (8-ethylquinoline-C,N) di (J.l-Cl) di-palladium lI, that contains an alkyl M-C bond, and other, the bis (N,N-dimethylbenzylamine-C,N) di (J.l-Cl) dipalladium lI, that contains an aryl M-C bonde The insertion reactions of isocyanides into the Pd-C bond occur with the last complex, but, insertion products of the 8-ethylquinoline derivates complexes only have been observed when a large excess of phenylisocyanide is used, and only polymerization products of isocyanide has been isolated.

Foi investigada a reação de inserção de isonitrilas (fenil-, o-toluil-, a-metilbenzil-, benzil- e terc-butil-) na ligação M-C dos seguintes complexos N-paladociclos: o bis (8-etilquinoleína-C,N) di (J..l-CI) dipaládio 11 e os seus derivados obtidos por substituição do grupo etila por outros grupos que contenham ligação M-C alquílica e, o bis (N,N-dimetilbenzilamina-C,N) di (J..l-Cl) dipaládio fi, que contém ligação M-C arílica. Enquanto que as reações de inserção de isonitrilas na ligação Pd-C ocorrem facilmente com o último complexo, produtos de inserção com os complexos derivados de 8-etilquinoleína só são observados quando um grande excesso de fenilisonitrila é empregado, e assim mesmo, somente produtos derivados de polimerização da isonitrila foram caracterizados. / We investigated the insertion reaction of some isocyanides (phenyl-, o-tolyl-, amethylbenzyl-, benzyl- and terc-butyl-) into M-C bond of two cyclopalladated complexes: the bis (8-ethylquinoline-C,N) di (J.l-Cl) di-palladium lI, that contains an alkyl M-C bond, and other, the bis (N,N-dimethylbenzylamine-C,N) di (J.l-Cl) dipalladium lI, that contains an aryl M-C bonde The insertion reactions of isocyanides into the Pd-C bond occur with the last complex, but, insertion products of the 8-ethylquinoline derivates complexes only have been observed when a large excess of phenylisocyanide is used, and only polymerization products of isocyanide has been isolated.

Le travail présenté dans ce memoire a été realisé au Laboratory of Molecular Catalysis (Chapitre 1, 2 et 3) de l'Universidade Federal do Rio Grande do Sul, sous la direction du Prof. Jaïrton Dupont, et au Laboratoire de Synthèse Métallo Induites (Chapitre 4) de l'Université de Strasbourg, sous la direction du Dr. Michel Pfeffer, entre le mois d'Aoüt 2006 et le mois de Décembre 2009. Le présent travail décrit la synthese et la caracterisation de nouvelles molecules п-extensibles contenant le noyau 2,1,3-benzothiadiazole (BID) et ses derives. Nous avons fait ('extension п des positions 4 et 7 de la BTD en utilisant les reactions de Suzuki et Sonogashira avec de bons rendements. Nous avons aussi bien caracterise ces nouveaux composes et etudie leurs caracteristiques electrochimiques et photophysiques. Nous avons étudié ('application des derives non symetriques de la BTD pour ('intercalation avec l'ADN. Pour les tests avec l'ADN, nous avons choisi trois composes ayant pour caractéristique commune un noyau BTD portant un groupe 4- methoxyphenyle, et dont nous avons fait varier la nature du substituant en position 7 : pyridine (2 et 3-pyridine) ou phenyle. Ces molécules ont donné d'excellents résultats lors de l'étude de leurs propriétés d'intercalation et de leurs propriétés photophysiques. Des nouvelles molécules cyclométallées ont été obtenues par la réaction des dérivés BTD avec l'acetate de palladium. Une série de complexes cyclopallades a pu être préparée avec de très bons rendements, sans que I'atome de soufre n'interagisse avec le metal. II est remarquable qu'il s'agisse de metallacycles a 6 chainons, moins courants que ceux a 5 chaînons. Tous les complexes ont 6t6 completement caractériéss, notamment par analyse élémentaire et par spectroscopie RMN, IR et UV-visible. Certains d'entre eux ont cristallises, et les monocristaux correspondants ont été analysés par diffraction des Rayons-X. / The present work was carried out at the Laboratory of Molecular Catalysis (Chapters 1, 2 and 3) in the Universidade Federal do Rio Grande do Sul, under supervision of Prof. JaIrton Dupont, and at the Laboratoire de Syntheses Metallo Induites (Chapter 4) at the Universite de Strasbourg, under supervision of Prof. Michel Pfeffer, between August 2006 and December 2009. In this work we describe the synthesis and characterisation of new Tr-extended molecules with the 2,1,3-benzothiadiazole core and their derivatives. We have performed the u extension of 4 and 7 positions of the BTD core employing Suzuki and Sonogashira reaction with good yields. The new molecules were fully characterized and their electrochemical and photophysical properties were investigated. Intercalation of the non symmetrical BTD derivatives and DNA were studied. Three molecules were chosen for testing the DNA intercalation, all compounds with the 4-methoxyphenyl group as the common ligand bound to one side of BTD core and a pyridine (2- or 3-pyridine) or a phenyl to the other side. We obtained excellent results for the intercalation and photophysical properties. New cyclometallated compounds were obtained by the reaction of palladium acetate and the BTD derivatives. A series of cyclopalladated compounds were synthesized with good yields with no interaction between the metal and sulphur atom. The remarkable characteristic of these cyclometallated compounds is the formation of 6 member rings, less commons than 5 members rings. All compounds were fully characterized by elemental analysis and NMR spectroscopy, IR and UV-Vis. Some complex were crystallized and analyzed by X-Ray diffraction.

Foi investigada a reação de inserção de isonitrilas (fenil-, o-toluil-, a-metilbenzil-, benzil- e terc-butil-) na ligação M-C dos seguintes complexos N-paladociclos: o bis (8-etilquinoleína-C,N) di (J..l-CI) dipaládio 11 e os seus derivados obtidos por substituição do grupo etila por outros grupos que contenham ligação M-C alquílica e, o bis (N,N-dimetilbenzilamina-C,N) di (J..l-Cl) dipaládio fi, que contém ligação M-C arílica. Enquanto que as reações de inserção de isonitrilas na ligação Pd-C ocorrem facilmente com o último complexo, produtos de inserção com os complexos derivados de 8-etilquinoleína só são observados quando um grande excesso de fenilisonitrila é empregado, e assim mesmo, somente produtos derivados de polimerização da isonitrila foram caracterizados. / We investigated the insertion reaction of some isocyanides (phenyl-, o-tolyl-, amethylbenzyl-, benzyl- and terc-butyl-) into M-C bond of two cyclopalladated complexes: the bis (8-ethylquinoline-C,N) di (J.l-Cl) di-palladium lI, that contains an alkyl M-C bond, and other, the bis (N,N-dimethylbenzylamine-C,N) di (J.l-Cl) dipalladium lI, that contains an aryl M-C bonde The insertion reactions of isocyanides into the Pd-C bond occur with the last complex, but, insertion products of the 8-ethylquinoline derivates complexes only have been observed when a large excess of phenylisocyanide is used, and only polymerization products of isocyanide has been isolated.

Le travail présenté dans ce memoire a été realisé au Laboratory of Molecular Catalysis (Chapitre 1, 2 et 3) de l'Universidade Federal do Rio Grande do Sul, sous la direction du Prof. Jaïrton Dupont, et au Laboratoire de Synthèse Métallo Induites (Chapitre 4) de l'Université de Strasbourg, sous la direction du Dr. Michel Pfeffer, entre le mois d'Aoüt 2006 et le mois de Décembre 2009. Le présent travail décrit la synthese et la caracterisation de nouvelles molecules п-extensibles contenant le noyau 2,1,3-benzothiadiazole (BID) et ses derives. Nous avons fait ('extension п des positions 4 et 7 de la BTD en utilisant les reactions de Suzuki et Sonogashira avec de bons rendements. Nous avons aussi bien caracterise ces nouveaux composes et etudie leurs caracteristiques electrochimiques et photophysiques. Nous avons étudié ('application des derives non symetriques de la BTD pour ('intercalation avec l'ADN. Pour les tests avec l'ADN, nous avons choisi trois composes ayant pour caractéristique commune un noyau BTD portant un groupe 4- methoxyphenyle, et dont nous avons fait varier la nature du substituant en position 7 : pyridine (2 et 3-pyridine) ou phenyle. Ces molécules ont donné d'excellents résultats lors de l'étude de leurs propriétés d'intercalation et de leurs propriétés photophysiques. Des nouvelles molécules cyclométallées ont été obtenues par la réaction des dérivés BTD avec l'acetate de palladium. Une série de complexes cyclopallades a pu être préparée avec de très bons rendements, sans que I'atome de soufre n'interagisse avec le metal. II est remarquable qu'il s'agisse de metallacycles a 6 chainons, moins courants que ceux a 5 chaînons. Tous les complexes ont 6t6 completement caractériéss, notamment par analyse élémentaire et par spectroscopie RMN, IR et UV-visible. Certains d'entre eux ont cristallises, et les monocristaux correspondants ont été analysés par diffraction des Rayons-X. / The present work was carried out at the Laboratory of Molecular Catalysis (Chapters 1, 2 and 3) in the Universidade Federal do Rio Grande do Sul, under supervision of Prof. JaIrton Dupont, and at the Laboratoire de Syntheses Metallo Induites (Chapter 4) at the Universite de Strasbourg, under supervision of Prof. Michel Pfeffer, between August 2006 and December 2009. In this work we describe the synthesis and characterisation of new Tr-extended molecules with the 2,1,3-benzothiadiazole core and their derivatives. We have performed the u extension of 4 and 7 positions of the BTD core employing Suzuki and Sonogashira reaction with good yields. The new molecules were fully characterized and their electrochemical and photophysical properties were investigated. Intercalation of the non symmetrical BTD derivatives and DNA were studied. Three molecules were chosen for testing the DNA intercalation, all compounds with the 4-methoxyphenyl group as the common ligand bound to one side of BTD core and a pyridine (2- or 3-pyridine) or a phenyl to the other side. We obtained excellent results for the intercalation and photophysical properties. New cyclometallated compounds were obtained by the reaction of palladium acetate and the BTD derivatives. A series of cyclopalladated compounds were synthesized with good yields with no interaction between the metal and sulphur atom. The remarkable characteristic of these cyclometallated compounds is the formation of 6 member rings, less commons than 5 members rings. All compounds were fully characterized by elemental analysis and NMR spectroscopy, IR and UV-Vis. Some complex were crystallized and analyzed by X-Ray diffraction.

Le travail présenté dans ce memoire a été realisé au Laboratory of Molecular Catalysis (Chapitre 1, 2 et 3) de l'Universidade Federal do Rio Grande do Sul, sous la direction du Prof. Jaïrton Dupont, et au Laboratoire de Synthèse Métallo Induites (Chapitre 4) de l'Université de Strasbourg, sous la direction du Dr. Michel Pfeffer, entre le mois d'Aoüt 2006 et le mois de Décembre 2009. Le présent travail décrit la synthese et la caracterisation de nouvelles molecules п-extensibles contenant le noyau 2,1,3-benzothiadiazole (BID) et ses derives. Nous avons fait ('extension п des positions 4 et 7 de la BTD en utilisant les reactions de Suzuki et Sonogashira avec de bons rendements. Nous avons aussi bien caracterise ces nouveaux composes et etudie leurs caracteristiques electrochimiques et photophysiques. Nous avons étudié ('application des derives non symetriques de la BTD pour ('intercalation avec l'ADN. Pour les tests avec l'ADN, nous avons choisi trois composes ayant pour caractéristique commune un noyau BTD portant un groupe 4- methoxyphenyle, et dont nous avons fait varier la nature du substituant en position 7 : pyridine (2 et 3-pyridine) ou phenyle. Ces molécules ont donné d'excellents résultats lors de l'étude de leurs propriétés d'intercalation et de leurs propriétés photophysiques. Des nouvelles molécules cyclométallées ont été obtenues par la réaction des dérivés BTD avec l'acetate de palladium. Une série de complexes cyclopallades a pu être préparée avec de très bons rendements, sans que I'atome de soufre n'interagisse avec le metal. II est remarquable qu'il s'agisse de metallacycles a 6 chainons, moins courants que ceux a 5 chaînons. Tous les complexes ont 6t6 completement caractériéss, notamment par analyse élémentaire et par spectroscopie RMN, IR et UV-visible. Certains d'entre eux ont cristallises, et les monocristaux correspondants ont été analysés par diffraction des Rayons-X. / The present work was carried out at the Laboratory of Molecular Catalysis (Chapters 1, 2 and 3) in the Universidade Federal do Rio Grande do Sul, under supervision of Prof. JaIrton Dupont, and at the Laboratoire de Syntheses Metallo Induites (Chapter 4) at the Universite de Strasbourg, under supervision of Prof. Michel Pfeffer, between August 2006 and December 2009. In this work we describe the synthesis and characterisation of new Tr-extended molecules with the 2,1,3-benzothiadiazole core and their derivatives. We have performed the u extension of 4 and 7 positions of the BTD core employing Suzuki and Sonogashira reaction with good yields. The new molecules were fully characterized and their electrochemical and photophysical properties were investigated. Intercalation of the non symmetrical BTD derivatives and DNA were studied. Three molecules were chosen for testing the DNA intercalation, all compounds with the 4-methoxyphenyl group as the common ligand bound to one side of BTD core and a pyridine (2- or 3-pyridine) or a phenyl to the other side. We obtained excellent results for the intercalation and photophysical properties. New cyclometallated compounds were obtained by the reaction of palladium acetate and the BTD derivatives. A series of cyclopalladated compounds were synthesized with good yields with no interaction between the metal and sulphur atom. The remarkable characteristic of these cyclometallated compounds is the formation of 6 member rings, less commons than 5 members rings. All compounds were fully characterized by elemental analysis and NMR spectroscopy, IR and UV-Vis. Some complex were crystallized and analyzed by X-Ray diffraction.

Resumo não disponível.

Resumo não disponível.

Resumo não disponível.

Este trabalho trata da reação de acoplamento Suzuki (reação entre haletos de arila ou benzila e ácidos arilborônicos) catalisada por compostos de paládio, e foi dividido em duas etapas. Na primeira etapa foi desenvolvido um sistema simples para a reação de Suzuki, em meio homogêneo, utilizando um sistema ternário de solventes (MeOH, PEO e n-heptano) (figura 1), que viabiliza o reciclo do catalisador por várias vezes. No sistema proposto foi utilizado como solvente a mistura metanol / poli( óxido de etileno), e no fmal da reação a bifenila formada foi extraída com solvente apoIar (n-heptano), com elevados rendimentos. Neste estudo, também foi possível obter produtos diferentes (rendimentos 70-80%) a cada reciclo, variando apenas o haleto de arila empregado no acoplamento. Na segunda etapa deste trabalho, foi desenvolvido um sistema para a realização do acoplamento Suzuki entre haletos de benzilas e ácidos arilborônicos catalisado por paládio. Durante o estudo de otimização foi possível verificar que estas reações ocorrem com baixa concentração de catalisador (0,002-1mol%), bem como constatou-se que o tempo de reação variou de 3h30min a 11horas, dependendo da quantidade de catalisador utilizado. O sistema se mostrou eficiente para reações com cloretos de benzila, levando a diarilmetanos com elevados rendimentos (>90%). A partir de reações competitivas se constatou que grupos substituintes no anel do haleto de benzila ou do ácido arilborônico não exercem influência estérica ou eletrônica significativa, bem como foi possível constatar que os brometos de benzilas são cinco vezes mais reativos que os cloretos de benzila. Finalmente, foi possível determinar uma reatividade relativa para os diferentes substratos halogenados frente à reação de Suzuki catalisada pelo sistema Pd(OAc)2IPPh3: (ArI > PhCH2Br > PhCH2CI > ArBr). / In this work the Pd-catalyzed Suzuki cross-coupling reaction of aryl halides or benzyl halides with aryl boronic acids was studied. In the first part of this work, we have fmd out that a system of poly (ethylene oxide) / methanol can be used as solvent medium for the Pd-catalyzed Suzuki cross-coupling reaction under mild condition. Afier the end of the reaction the product is extracted with heptane and the polar phase can be reused several without any change in the activity (Fig.1). Pure biaryl products are obtained from the no polar phase in excellent isolated yields (>90%). The same catalyst-containing polar phase was used to coupling different aryl halides, furnishing the products in good to high isolated yields (70-80%). In the second part of we have developed a simple and efficent catalytic system for the Suzuki cross-coupling reaction of benzyl halides (bromides and chlorides) with aryl boronic acids. The catalyst precursor is prepared in situ from palladium acetate and triphentylphosphine showing high activity for reaction of benzylic bromides and chlorides with arylboronic acids. The reaction can be carried out at low catalys loading (0.002 - lmol%) and under mild conditions (80°C), furnishing diarylmethane derivatives in high yelds (86-99%). Compared with the aryl halides, the Suzuki crosscoupling reaction of benzyl chlorides is much less sensitive to steric and electronic effects. On the other hand, as observed the aryl halides, the cross-coupling reaction of benzyl bromide is five times faster than the coupling of benzyl chlorides. Finally we have obtained a relative reactive for the Pd(OAchIPPh3- catalyzed Suzuki cross coupling reaction: ArI> ArCH2Br > ArCH2Cl > ArBr.