El desarrollo de nuevos catalizadores solubles en agua, así como el estudio de su aplicación a distintas transformaciones químicas, sus propiedades fisicoquímicas y su potencial recuperación, es un aporte muy significativo a la catálisis organometálica, y a la química orgánica en general. La presente Tesis, organizada en cinco capítulos, comprende la síntesis, caracterización y aplicaciones de 12 complejos de oro(I) con ligandos carbeno Nheterocíclico (NHC) derivados del imidazol (capítulos 1-4) y un resumen de los resultados obtenidos en una estancia doctoral realizada en el exterior (capítulo 5). En el capítulo 1 se describen las metodologías sintéticas llevadas a cabo para la generación de los ligandos y sus correspondientes complejos, así como el estudio de su estabilidad en medio acuoso. De los complejos sintetizados, seis de ellos contienen grupos sulfonato en su estructura y los restantes son neutros, por lo que mediante el tratamiento con KPF6 o AgSCN, rinden las correspondientes especies iónicas. La caracterización se realizó mediante técnicas complementarias (RMN, FT-IR, UV-Vis, EM) y, en el caso de los complejos, en colaboración con los Dres. Marcelo Ceolín y Agustín Picco (INIFTA-La Plata), se empleó la Espectroscopía de Absorción de Rayos X de Estructura Fina (XAFS). El capítulo 2 trata sobre un exhaustivo estudio catalítico, en medio acuoso, de los complejos sintetizados así como su reciclaje y reutilización. La especie activa fue generada por tres vías diferentes: i) térmica; ii) empleando sales de plata; iii) mediante la asistencia de radiación de microondas o ultrasonido. En colaboración con la Dra. Viviana Dorn (INQUISUR-UNS) se realizaron cálculos teóricos que apoyan los resultados experimentales obtenidos. Por otro lado, teniendo en cuenta la inestabilidad de ciertos complejos, en colaboración con el grupo del Dr. Mariano Correa (UNRC), se estudió la generación de Au-NPs y su estabilización con sales de imidazolio sulfonadas (capítulo 3). En el capítulo 4, teniendo en cuenta la hidrofilia de los complejos sulfonados, se evaluó su eficacia antibacterial frente a bacterias Gram+ y Gram-, en comparación con sus respectivos ligandos. Los estudios biológicos fueron realizados en colaboración con las Dras. M. Soledad Vela Gurovic (CERZOS) y Nelda Olivera (CENPAT). Finalmente, el capítulo 5 describe la síntesis de 5 complejos de oro(I) generados a partir de indazoles y 3 conteniendo fosfinas, junto con los resultados preliminares obtenidos en la cicloisomerización de eninos. Este trabajo fue realizado en colaboración con el Dr. Javier Carreras (ICIQ), bajo la supervisión del Dr. Antonio M. Echavarren (ICIQ). / The development of new water-soluble catalysts and the study of their application to different chemical transformations, physicochemical properties and potential recovery is a very significant contribution to organometallic catalysis, and organic chemistry in general. This thesis, organized in five chapters, includes the synthesis, characterization and applications of 12 gold(I) complexes with imidazole-derived N-heterocyclic carbene (NHC) ligands (Chapters 1-4) and a summary of the results obtained in a doctoral stay abroad (chapter 5). In Chapter 1, synthetic methodologies carried out for the generation of the ligands and their corresponding complexes and the study of its stability in aqueous medium are described. Six complexes contain sulphonate groups in its structure and the rest are neutral, which by treatment with AgSCN or KPF6, generate the corresponding ionic species. The characterization was done by complementary techniques (NMR, FT-IR, UV-Vis, MS) and, in the case of complexes, in collaboration with Dr. Marcelo Ceolín and Agustin Picco (INIFTA-La Plata), Spectroscopy X-ray absorption fine-structure (XAFS) was used. Chapter 2 deals with a comprehensive catalytic study in aqueous medium of the complexes synthesized, and their recycling and reuse. The active species was generated by three different ways: i) heating; ii) silver salts; iii) microwave radiation or ultrasound assistance. Theoretical studies, in collaboration with Dr. Viviana Dorn, support the experimental results. On the other hand, considering the instability of certain complexes, in collaboration with Dr. Mariano Correa (UNRC), the generation of Au-NPs and their stabilization with sulphonated imidazolium salts, was studied (Chapter 3). In Chapter 4, considering the hydrophilicity of sulphonated complexes, its antibacterial effectiveness against Gram + and Gram- bacteria, compared to their respective ligands, was evaluated. Biological studies were conducted in collaboration with Dr. M. Soledad Vela Gurovic (CERZOS) and Nelda Olivera (CENPAT). Finally, Chapter 5 describes the synthesis of 5 complexes of gold(I) generated from indazoles and 3 containing phosphines, as well as preliminary results obtained in cycloisomerization of enynes. This work was performed in collaboration with Dr. Javier Carreras (ICIQ), under the supervision of Dr. Antonio M. Echavarren (ICIQ).

Made available in DSpace on 2016-06-02T20:34:14Z (GMT). No. of bitstreams: 1 2090.pdf: 4236088 bytes, checksum: b76d653a03c3abe6efb7293b1d27393b (MD5) Previous issue date: 2007-03-29 / Universidade Federal de Minas Gerais / ON THE RUTHENIUM PHOSPHINIC COMPLEXES: HYDROGENATION, ROMP-HYDROGENATION is a concise explanation about the ruthenium chemistry with donor bulky electron-rich biphosphines as precursor unity to prepare ruthenium carbon moiety. The complexes synthesized were applied as precatalyst on the hydrogenation of double bonds and non polar double bonds, as well as precatalyst on the assisted tandem catalyses of cyclooctene, ROMP Hydrogenation. The dihydride complex [RuH(dtbpm)]2-μ- (Cl)2 have been applied with good results as a precatalyst at mild conditions to hydrogenate polar and non polar double bonds, and remarkable activity over a substrate containing both kind of bonds. The regioseletivity can be managed by simple modification on the variable conditions of the system, applying different solvent, auxiliary ligands trigged on the course of the reaction, and addition of co-catalyst. By the way, the complex [RuH(dtbpm)]2-μ-(Cl)2 is a powerful precursor to afford new hydride complexes containing ruthenium. In the fact of this view, the complex [RuHCl(dtbpm)(bipy)] achieved from [RuH(dtbpm)]2-μ-(Cl)2 is the first mono hydride complex, that is active on the reduction of acetophenone without base conditions. The photochemistry behaviour of the vinylidene complexes containing ruthenium II obtained from the isomerization and -η2 coordination of the phenylacetylene was studied, with special attention to the complex [RuCl2(PPh3)2(bipy)(=C=CHPh)](PF6), which presents an intense emission centrated at 460 nm, when excitated between 300 400 nm at room temperature. The first coordination of the ligand 1-tert-butil-3-(di-tertbutilphosphinomethyl) imidazol-2-ilidene (CNCP) on the ruthenium centre is describing to afford the complex [RuCl(CNCP-κ2(C2,P))]2-μ-(Cl)2.The last one is a well defined binuclear ruthenium (II) complex with 16 electron valence in two chloride bridge, stabilized by the bulky, electron-rich chelating ligand (CNCP). / COMPLEXOS FOSFÍNICOS DE RUTÊNIO: HIDROGENAÇÃO, ROMPHIDROGENAÇÃO é uma descrição concisa da química de compostos de rutênio visando à utilização de bifosfinas quelantes doadoras de densidade eletrônica como unidade precursora para a formação da ligação rutênio - carbono. Os complexos sintetizados foram aplicados como pré-catalisadores na hidrogenação de duplas polares e apolares, assim como na tandem catálise assistida do cicloocteno, ROMP hidrogenação. O complexo dihidreto [RuH(dtbpm)]2-μ-(Cl)2 demonstrou ser um bom catalisador para a hidrogenação de duplas polares e apolares em condições brandas, assim como um catalisador versátil para a hidrogenação de substratos contendo duplas mistas, podendo-se controlar a regiosseletividade através das variáveis do sistema, como solvente, ligantes auxiliares e co-catalisadores, além deste ser um ótimo precursor de síntese para novos hidretos contendo rutênio. Neste sentido, o complexo [RuHCl(dtbpm)(bipy)] obtido do [RuH(dtbpm)]2-μ-(Cl)2 é o primeiro mono hidreto contendo uma difosfina, isolado e caracterizado, ativo na redução da acetofenona, sem a presença de base. O comportamento fotoquímico de complexos vinilidênicos contendo rutênio II, obtidos a partir da isomerização e coordenação -η2 do fenilacetileno foram estudados, com especial atenção ao complexo [RuCl2(PPh3)2(bipy)(=C=CHPh)](PF6), que quando excitado em 300 400 nm a temperatura ambiente em solução (CH2Cl2 ou CH3CN) produz uma intensa emissão centrada em 460 nm. A primeira coordenação do ligante 1-tertbutil- 3-(di-tert-butilfosfinometil)imidazol-2-ilideno CNCP ao átomo de rutênio é apresentada para a formação do complexo [RuCl(CNCP-κ2(C2,P))]2-μ-(Cl)2. Este é um dinuclear de rutênio(II) com 16 elétrons na camada de valência em ponte com dois átomos de cloro, estabilizado por um ligante volumoso quelante rico em elétrons

Aquesta tesi doctoral es basa en l'estudi de l'aplicació en catàlisi de dos tipus de complexos organometallics basats en dos metalls de tansició diferents. Concretament s'estudien complexos macrocíclics triolefínics de pal·ladi(0) com a catalitzadors per a les reaccions de Suzuki i Heck, i oxocomplexos carbènics de ruteni(II) com a espècies catalítiques en oxidacions de compostos orgànics. En el cas dels complexos de ruteni s'ha vist que en augmentar el nombre de lligands carbènics en l'esfera de coordinació del metall s'aconseguiex afavorir els processos bielectrònics, obtenint-se catalitzadors més actius i més selectius.En un segon pas, els dos tipus de catalitzadors homogenis s'han immobilitzat sobre la superfície d'un elèctrode mitjançant l'estratègia d'electropolimerització del grup pirrol. Els elèctodes modificats resultants s'han aplicat com a catalitzadors heterogenis. En ambdós casos els catalitzadors heterogenis han mostrat una activitat equiparable o superior a la del sistema homogeni corresponent.Finalment, s'ha assajat una reacció de catàlisi tàndem en què els dos catalitzadors (immobilitzats sobre el mateix elèctrode) actuen en cooperació. S'ha aconseguit realitzar dues transformacions consecutives d'un substat orgànic. / This thesis studies the application in catalysis of two types of organometallic complexes based on two different transition metals. Concretely, we have studied the application of palladium triolefinic macrocyclic complexes as catalysts in the Suzuki and Heck reactions, and the application of ruthenium carbenic aquacomplexes as catalysts in the oxidation of organic substrates. For Ru complexes we have seen that the more carbenic groups in the coordination sphere, the more favored is a bielectronic process, that meaning a better catalytic activity and selectivity.In a second step, both catalysts have been immobilized on an elecctrode surface by pyrrole electropolymerization. The resulting modified electrodes have been used as heterogeneous catalysts, showing a similar or a better activity that the corresponding homogeneous systems.Finally, We have designed and tested a tandem reaction with both catalysts (immobilized on the same electrode) acting in cooperation. We have been able to realize two consecutive transformations of an organic substrate.