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Submitted by GABRIELA FRANCINI BOZZA RICCI null (gabrielafrancini@gmail.com) on 2018-09-28T02:39:14Z No. of bitstreams: 1 Ricci_GFB-Tese_2018.pdf: 17373855 bytes, checksum: 90d67387576c4e8408e13aecc7dcc8ac (MD5) / Approved for entry into archive by Ana Carolina Gonçalves Bet null (abet@iq.unesp.br) on 2018-09-28T13:20:11Z (GMT) No. of bitstreams: 1 ricci_gfb_dr_araiq_int.pdf: 17344506 bytes, checksum: 2c9d3a77dca087440b81022ef3bed113 (MD5) / Made available in DSpace on 2018-09-28T13:20:11Z (GMT). No. of bitstreams: 1 ricci_gfb_dr_araiq_int.pdf: 17344506 bytes, checksum: 2c9d3a77dca087440b81022ef3bed113 (MD5) Previous issue date: 2018-09-14 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Ciclopaladados constituem uma classe de organometálicos de grande interesse, sobretudo por suas extensas aplicações em diversas áreas da Química. Dentre os compostos susceptíveis a reação de ortometalação destacam-se as oximas, onde apesar do frequente emprego de complexos ciclopaladados contendo derivados das oximas, como catalisadores ou pré-catalisadores eficientes, pouco se sabe sobre as potencialidades biológicas dos mesmos. Foram sintetizados doze compostos quelatos de paládio inéditos pela clivagem em ponte de compostos do tipo [PdCl(C2,N-oxima)]2 e fosfinas terciárias (L) {C2,N-oxima = acetofenonaoxima ou benzaldeidoxima; L = trifenilfosfina (PPh3), tri(p-toluil)fosfina (tpf), tris-(4-fluorfenilfosfina) (tfpp), tris-(4-metoxifenil)fosfina (tmf), difenil-(p-toluil)-fosfina (dpt) e triciclohexilfosfina (PCy3)}. Os compostos foram caracterizados por análise elementar, análise térmica (termogravimétrica e diferencial), espectroscopia vibracional na região do infravermelho e espectroscopia de ressonância magnética nuclear de 1H, 13C e 31P. As estruturas cristalinas e moleculares de nove compostos foram determinadas por difratometria de raios X de monocristal, onde [PdCl(C2,N-afox)(L)], onde {L = (PPh3), (tfpp), (tmf), (dpt) e (PCy3)} e [PdCl(C2,N-bzox)(L)], em que {L = (PPh3), (tpf), (tfpp) e (PCy3)}. Além disso, cálculos da superfície de Hirshfeld foram realizados para explorar a natureza e as principais contribuições de diferentes contatos intermoleculares na estabilidade do empacotamento do cristal. Experimentos preliminares para determinar o potencial citotóxico dos compostos foram realizados frente a MCF-7 (adenocarcinoma mamário humano), LM3 (adenocarcinoma mamário murino), A549 (adenocarcinoma epitelial de pulmão humano) e MCR5 (fibroblasto de pulmão humano) e ensaios preliminares a respeito da atividade inibitória frente as catepsinas B e L também foram avaliados, sugerindo um possível modo de ação para os compostos obtidos e testados. / Cyclopalladated complexes represent an interesting class of organometallic compounds, mainly for their extensive uses in several areas of Chemistry. Among the organic compounds prone to orthometallation reaction, oximes have attracted considerable attention since their cyclopalladated derivatives have been employed as catalysts in many organic reactions. Despite the intensive work on this area, studies on the biological activity of these compounds remain scarce in the literature. In this context, this work deals with the synthesis, spectroscopic and structural investigation on a series of cyclopalladated compounds of general formulae [PdCl(C2,N-oxime)(L)] (C2,N-oxime = orthometallated acetophenoneoxime (afox) or benzaldehydeoxime (bzox); L = monodentate phosphines). Bridge-splitting reactions between [Pd(C2,N-oxime)(μ-Cl)]2 and phosphines (L = triphenylphosphine (PPh3), tri(p-tolyl)phosphine (tpf), tris(4-fluorophenyl)phosphine (tfpp), tris-(4-methoxyphenyl)phosphine (tmf), diphenyl(p-tolyl)phosphine (dpt) and tricyclohexylphosphine (PCy3)} in a 1:2 ratio, yielded neutral mononuclear cyclopalladated compounds of the type [PdCl(C2,N-oxime)(L)]. The compounds have been characterized by elemental analyses, IR and 1H-, 13C and 31P{1H}-NMR spectroscopies, and thermal analysis TG-DTA. The crystal and molecular structures of the compounds [PdCl(C2,N-afox)(L)] {L = (PPh3), (tfpp), (tmf), (dpt) and (PCy3)} and [PdCl(C2,N-bzox)(L)] { L = (PPh3), (tpf), (tfpp) and (PCy3)} have been determined by single-crystal X-ray diffraction. Hirshfeld surface calculations have been carried out to explore the nature and major contributions of different intermolecular contacts towards crystal packing stability. Preliminary cytotoxic evaluation of the compounds towards MCF-7 (human breast adenocarcinoma), LM3 (murine mammary adenocarcinoma), A549 (human lung epithelial adenocarcinoma) and MCR5 (human lung fibroblast) have been carried out. The ability of the compounds to induce the inhibition of cathepsins B and L have also been evaluated in this work. / CAPES: 1570789

FRANCISCO, Thiago dos Santos. Complexos Fosfínicos de Rutênio: Síntese, Caracterização, Imobilização e Atividade Catalítica. 2015. 146 f. Tese (doutorado em química)- Universidade Federal do Ceará, Fortaleza-CE, 2015. / Submitted by Elineudson Ribeiro (elineudsonr@gmail.com) on 2016-04-05T17:50:35Z No. of bitstreams: 1 2016_tese_tsfrancisco.pdf: 4355005 bytes, checksum: d6b9963db1d94445234858ad160bdbae (MD5) / Approved for entry into archive by José Jairo Viana de Sousa (jairo@ufc.br) on 2016-05-20T18:38:15Z (GMT) No. of bitstreams: 1 2016_tese_tsfrancisco.pdf: 4355005 bytes, checksum: d6b9963db1d94445234858ad160bdbae (MD5) / Made available in DSpace on 2016-05-20T18:38:15Z (GMT). No. of bitstreams: 1 2016_tese_tsfrancisco.pdf: 4355005 bytes, checksum: d6b9963db1d94445234858ad160bdbae (MD5) Previous issue date: 2015 / The results presented in this thesis involve the synthesis of coordination compounds containing phosphine ligands and redox active (non-innocent ligands) in the ruthenium coordination sphere. This work is part of a research line of Bioinorganic Group research aimed, as the ultimate goal, the application of the isolated compounds in catalysis of hydrogenation reactions. During the development of PhD activities, from March 2010 to January 2015, six compounds (06) unpublished in the literature were synthesized; one of which being classified as a precursor complex, [RuIICl2(binap)(PPh3)], where binap = 2,2′-bis(diphenylphosphine)-1,1′-dinaphthalene. All of these complexes were characterized by means of phosphorous nuclear resonance magnetic (RMN 31P{1H}), elemental analysis, infrared spectroscopy and electronic spectroscopy in the ultraviolet and visible regions. Despite several attempts to produce crystals of the synthesized compounds, only the trans-[RuIICl2(dppb)(opda-Clcat)] complex, where dppb = 1,4-bis(diphenylphosphine)butane and opda-Clcat = 4-cloro-1,2-phenylenediamine, yielded suitable crystals for determination of X-ray structure. From the results obtained during the cited time, two papers were published in indexed journals ((Polyhedron 2010, 29, 3349–3354 and Polyhedron 2012, 31, 104–109) and five works were shown in national and international meetings. The RMN 31P{1H} spectra of the isolated compounds presented only one signal indicating that the phosphorous atoms lie in equivalent positions and trans in relation to the donor atoms of the non-innocent ligands. For the trans-[RuIICl2(dppb)(opda-Clcat)] complex, however, a dublet of dublet was observed and was assigned to the assimetry of the opda-Cl moiety, which was confirmed by X ray diffraction. The electronic spectroscopic data indicated the oxidized state of the o-phenylene ligands upon coordination to the metal atom thus making possible the back-bonding interaction. The catalytic activity assays were monitored by gas chromatography coupled to mass spectrometry using the standard hydrogenation reaction of the alcohol molecule acetophenone to 1-phenyl ethanol. In addition to the complex originally presented in this thesis, [RuIICl2(binap)(PPh3)](1), trans-[RuIICl2(binap)(opda-Clcat)](2), trans-[RuIICl2(binap)(fenantq)](3), trans-[RuIICl2(PPh3)2(opdaq)](5) and trans-[RuIICl2(PPh3)2(fenantq)](6), where fenantq and opdaq are, respectively, 9,10-phenanthraquinone and 1,2-phenylenediamine, such assays were also carried out for compounds which were previously synthesized during the master course and by other researchers of the Bioinorganic Group resulting resulting in a total of twenty (20) studied catalysts. Among these complexes, two were studied in heterogeneous condition upon immobilization on hybrid spheres of silica chitosan. By accounting for all the studied conditions, the highest values of conversion (> 90%) were observed for trans-[RuIICl2(dppb)(Quinone)](10), cis-[RuIICl2(dppb)(opda-Clq)](13), trans-[RuIICl2(dppb)(tabq,cat)](15) and cis-[RuIICl2(dppb)(tabq,cat)](16), where tabq,cat = 3,3’,4,4’-tetraaminobiphenyls. The values of conversion observed for the heterogeneous systems, c.a. 60%, although lower than those calculated for the homogeneous systems under similar conditions, do not constitute a disadvantage, since separation step is no longer needed. The compounds that showed the higher conversion values in homogeneous medium feature in common the presence of non-innocent ligands in the oxidized state. This observation indicates, very probably, two synergistic effects which influence the affinity of the substrate: (i) the increase of the Lewis acidity of the metal by the oxidation of the ligand and (ii) the function of electron density reservoir of the redox active ligand that allows the metal to store (donate) electron density from (to) the ligand during the elementary steps of the catalytic cycle by preventing excessive charge density on the metal. / Os resultados apresentados neste trabalho envolvem a síntese de compostos de coordenação contendo fosfinas e ligantes redox ativos (ligantes não-inocentes) na esfera de coordenação do rutênio. Este trabalho está inserido em uma linha de pesquisa do Grupo de Bioinorgânica que visa, como objetivo final, a aplicação dos compostos isolados na catálise de reações de hidrogenação. Durante o desenvolvimento das atividades de doutorado, período de março de 2010 a janeiro de 2015, foram sintetizados seis (06) compostos inéditos na literatura, um dos quais sendo classificado como complexo precursor, [RuIICl2(binap)(PPh3)], onde binap = 2,2′-bis(difenilfosfina)-1,1′-dinaftaleno. Todos estes compostos foram caracterizados por ressonância magnética nuclear de fósforo (RMN 31P{1H}), análise elementar e espectroscopias vibracional na região do infravermelho e eletrônica nas regiões do ultravioleta e visível. A despeito das diversas tentativas de formação de cristais dos complexos isolados, apenas o composto trans-[RuIICl2(dppb)(opda-Clcat)], onde dppb = 1,4-bis(difenilfosfina)butano e opda-Clcat = 4-cloro-1,2-fenilenodiamina, forneceu cristais passíveis de análise por difração de raios X. A partir dos resultados obtidos durante o período citado, dois trabalhos foram publicados em periódicos indexados (Polyhedron 2010, 29, 3349–3354 e Polyhedron 2012, 31, 104–109) e cinco trabalhos foram apresentados em congressos nacionais e internacionais. Os espectros de RMN 31P{1H} dos compostos sintetizados apresentaram um único sinal indicando que os átomos de fósforo ocupam posições equivalentes e trans aos átomos doadores dos ligantes não-inocentes. Apenas o composto trans-[RuIICl2(dppb)(opda-Clcat)] apresentou um dubleto de dubleto que foi atribuído à assimetria do ligante opda-Cl, sendo confirmado pelos dados de difração de raios X. Os dados de espectroscopia eletrônica indicaram o estado oxidado dos ligantes o-fenilênicos após coordenação ao centro metálico sendo possível, portanto, a observação de interações de retrodoação. Os ensaios de atividade catalítica foram monitorados por cromatografia gasosa acoplada à espectrometria de massa utilizando a reação padrão de hidrogenação da molécula de acetofenona ao álcool 1-feniletanol. Além dos complexos originalmente apresentados nesta tese, [RuIICl2(binap)(PPh3)](1), trans-[RuIICl2(binap)(opda-Clcat)](2), trans-[RuIICl2(binap)(fenantq)](3), trans-[RuIICl2(PPh3)2(opdaq)](5) e trans-[RuIICl2(PPh3)2(fenantq)](6), onde fenantq e opdaq são, respectivamente, 9,10-fenantrequinona e 1,2-fenilenodiamina, tais ensaios foram, também, realizados com compostos previamente sintetizados durante a dissertação de mestrado e por outros membros do Grupo de Bioinorgânica, resultando em um total de vinte (20) catalisadores estudados. Destes complexos, dois foram estudados em condições heterogêneas após imobilização sobre esferas híbridas de sílica/quitosana. Dentre os sistemas estudados, os complexos trans-[RuIICl2(dppb)(Quinone)](10), cis-[RuIICl2(dppb)(opda-Clq)](13), trans-[RuIICl2(dppb)(tabq,cat)](15) e cis-[RuIICl2(dppb)(tabq,cat)](16), onde tabq,cat = 3,3’,4,4’-tetraaminobifenil, apresentaram os mais altos valores de conversão (> 90%) em todas as condições analisadas. Os valores de conversão observados para os sistemas heterogêneos, ~ 60%, embora menores que aqueles calculados para os sistemas homogêneos em condições similares, não representam desvantagem, uma vez que implicam na redução da etapa de separação. Os compostos que apresentaram maiores valores de conversão em meio homogêneo apresentam, em comum, a presença de ligantes não-inocentes no estado oxidado. Essa observação indica a presença de efeitos sinérgicos que influenciam na afinidade do substrato, a citar: (i) aumento da acidez de Lewis do metal pela oxidação do ligante e (ii) função de reservatório de densidade eletrônica do ligante redox ativo que permitir o metal estocar (doar) densidade eletrônica no (para o) ligante durante as etapas elementares do ciclo catalítico, evitando a localização excessiva de carga sobre o metal. / The results presented in this thesis involve the synthesis of coordination compounds containing phosphine ligands and redox active (non-innocent ligands) in the ruthenium coordination sphere. This work is part of a research line of Bioinorganic Group research aimed, as the ultimate goal, the application of the isolated compounds in catalysis of hydrogenation reactions. During the development of PhD activities, from March 2010 to January 2015, six compounds (06) unpublished in the literature were synthesized; one of which being classified as a precursor complex, [RuIICl2(binap)(PPh3)], where binap = 2,2′-bis(diphenylphosphine)-1,1′-dinaphthalene. All of these complexes were characterized by means of phosphorous nuclear resonance magnetic (RMN 31P{1H}), elemental analysis, infrared spectroscopy and electronic spectroscopy in the ultraviolet and visible regions. Despite several attempts to produce crystals of the synthesized compounds, only the trans-[RuIICl2(dppb)(opda-Clcat)] complex, where dppb = 1,4-bis(diphenylphosphine)butane and opda-Clcat = 4-cloro-1,2-phenylenediamine, yielded suitable crystals for determination of X-ray structure. From the results obtained during the cited time, two papers were published in indexed journals ((Polyhedron 2010, 29, 3349–3354 and Polyhedron 2012, 31, 104–109) and five works were shown in national and international meetings. The RMN 31P{1H} spectra of the isolated compounds presented only one signal indicating that the phosphorous atoms lie in equivalent positions and trans in relation to the donor atoms of the non-innocent ligands. For the trans-[RuIICl2(dppb)(opda-Clcat)] complex, however, a dublet of dublet was observed and was assigned to the assimetry of the opda-Cl moiety, which was confirmed by X ray diffraction. The electronic spectroscopic data indicated the oxidized state of the o-phenylene ligands upon coordination to the metal atom thus making possible the back-bonding interaction. The catalytic activity assays were monitored by gas chromatography coupled to mass spectrometry using the standard hydrogenation reaction of the alcohol molecule acetophenone to 1-phenyl ethanol. In addition to the complex originally presented in this thesis, [RuIICl2(binap)(PPh3)](1), trans-[RuIICl2(binap)(opda-Clcat)](2), trans-[RuIICl2(binap)(fenantq)](3), trans-[RuIICl2(PPh3)2(opdaq)](5) and trans-[RuIICl2(PPh3)2(fenantq)](6), where fenantq and opdaq are, respectively, 9,10-phenanthraquinone and 1,2-phenylenediamine, such assays were also carried out for compounds which were previously synthesized during the master course and by other researchers of the Bioinorganic Group resulting resulting in a total of twenty (20) studied catalysts. Among these complexes, two were studied in heterogeneous condition upon immobilization on hybrid spheres of silica chitosan. By accounting for all the studied conditions, the highest values of conversion (> 90%) were observed for trans-[RuIICl2(dppb)(Quinone)](10), cis-[RuIICl2(dppb)(opda-Clq)](13), trans-[RuIICl2(dppb)(tabq,cat)](15) and cis-[RuIICl2(dppb)(tabq,cat)](16), where tabq,cat = 3,3’,4,4’-tetraaminobiphenyls. The values of conversion observed for the heterogeneous systems, c.a. 60%, although lower than those calculated for the homogeneous systems under similar conditions, do not constitute a disadvantage, since separation step is no longer needed. The compounds that showed the higher conversion values in homogeneous medium feature in common the presence of non-innocent ligands in the oxidized state. This observation indicates, very probably, two synergistic effects which influence the affinity of the substrate: (i) the increase of the Lewis acidity of the metal by the oxidation of the ligand and (ii) the function of electron density reservoir of the redox active ligand that allows the metal to store (donate) electron density from (to) the ligand during the elementary steps of the catalytic cycle by preventing excessive charge density on the metal.

Submitted by Bruna Rodrigues (bruna92rodrigues@yahoo.com.br) on 2016-10-05T13:03:51Z No. of bitstreams: 1 DissWJVP.pdf: 10066603 bytes, checksum: ffd7ae5b27438d4e59ea8f95fc995f39 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-20T16:12:19Z (GMT) No. of bitstreams: 1 DissWJVP.pdf: 10066603 bytes, checksum: ffd7ae5b27438d4e59ea8f95fc995f39 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-20T16:12:25Z (GMT) No. of bitstreams: 1 DissWJVP.pdf: 10066603 bytes, checksum: ffd7ae5b27438d4e59ea8f95fc995f39 (MD5) / Made available in DSpace on 2016-10-20T16:12:32Z (GMT). No. of bitstreams: 1 DissWJVP.pdf: 10066603 bytes, checksum: ffd7ae5b27438d4e59ea8f95fc995f39 (MD5) Previous issue date: 2013-03-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / In this work were synthesized and characterized complexes of general formule [Pt(P)2Cl2] and [Pt(P)2(CQ)Cl]PF6 (where (P)2= triphenylphosphine (PPh3), 1,3-bis (diphenylphosphino ) propane (dppp), 1,4-bis (diphenylphosphino) butane (dppb), 1,1 '-bis (diphenylphosphino) ferrocene (dppf) and CQ = Chloroquine). The characterization of the complexes was performed by means of elemental analysis, conductivity, absorption spectroscopy in the infrared and UV-Visible regions (IR and UV-Vis), NMR 1H, 13C{1H}, 15N{1H}, 31P{1H}, 195Pt{1H}, cyclic voltammetry and differential pulse, and mass spectrometry (in the case of chloroquine complexes). Also, the interaction of the chloroquine complexes with DNA was evaluated for calculate to the magnitude of the interaction with this important macromolecule, obtaining that the complexes showed interaction constants similar and higher than those presented by CQ and CQDP, and decrease the relative viscosity of DNA. We also evaluated the cytotoxic activity of the chloroquine complexes in the cell lines MCF-7 and MDA-MB-231 (human breast tumor cell lines), DU-145 (the human prostate tumor cell line), A549 (the human lung adenocarcinoma epithelial cell line), V79-4 (the Chinese hamster lung fibroblast cell line), and the L929 (nontumor cell line from mice), showed promissory activity, mainly of the complexes 5 and 8. / Neste trabalho, realizou-se as síntese e caracterizações dos complexos de formula geral [Pt(P-P)Cl2] e [Pt(P-P)(CQ)Cl]PF6 (onde P-P= trifenilfosfina (PPh3), 1,3-bis(difenilfosfino)propano (dppp), 1,4- bis(difenilfosfino)butano (dppb), 1,1´-bis(difenilfosfino)ferroceno (dppf), e CQ=Cloroquina). As caracterizações foram realizadas por meio de analise elementar, condutividade, espectroscopia de absorção na região do infravermelho (IV), de RMN 1H, 13C{1H}, 15N{1H}, 31P{1H}, 195Pt{1H}, espectroscopia de absorção na região do UV-Visível, voltametria cíclica e pulso diferencial, e espectrometria de massas (no caso dos complexos com CQ). Também foi avaliada a interação dos complexos sintetizados com o ADN, com a finalidade de estimar a magnitude da interação dos complexos sintetizados com esta importante macromolécula, obtendo se que os complexos sintetizados apresentam constantes de interação similares e superiores as apresentadas pela CQ e CQDF, e diminuem viscosidade relativa do DNA. Também foi avaliada a atividade citotóxica dos complexos com CQ nas linhagens celulares tumorais MCF-7 e MDA-MB-231 (tumor de mama humano), DU-145 (tumor de próstata humano), A549 (adenocarcinoma de pulmão humano) e não tumorais V79-4 (fibroblasto de pulmão de hamster chinese) e L929 (células não tumorais de camundongo), os quais apresentarem atividade promissória, principalmente os complexos 5 e 8.

[ES] En la presente tesis doctoral se ha llevado a cabo un estudio de nuevas reacciones orgánicas de interés catalizadas por diferentes especies de paladio, tanto clústeres como complejos metálicos. En primer lugar, se ha estudiado la reacción intramolecular regioirregular de Mizoroki-Heck catalizada por clústeres de paladio en disolución, donde se han puesto en conflicto las propiedades electrónicas y estéricas de la reacción de Mizoroki-Heck, obteniendo la reacción de ciclación con una regioselectividad inversa. También se han realizado estudios mecanísticos mediante experimentos cinéticos y computacionales. También se ha desarrollado un catalizador sólido basado en una zeolita, concretamente la zeolita X, que tras intercambiar los cationes de compensación de carga e introducir el Pd, cataliza la reacción intermolecular de Mizoroki-Heck regioirregular. Se ha conseguido obtener un centro activo en la zeolita con las condiciones tanto estéricas como electrónicas óptimas para realizar la reacción intermolecular regioirregular de Mizoroki-Heck entre estirenos y iodobencenos, con buenos rendimientos y selectividades. Por otro lado, se ha estudiado una nueva ruta de síntesis de una fragancia comercial, la deshidromuscona, donde se obtiene un rendimiento global de síntesis mayor que el obtenido actualmente en la industria, todo ello en un menor número de pasos. Se ha llevado a cabo un estudio más intenso sobre el paso donde se realiza la macrociclación en alta concentración, para poder ser viable industrialmente. Mediante la reacción de Mizoroki-Heck estudiada arriba, se ha llevado a cabo un estudio de macrociclación a alta concentración donde, a partir de unos sustratos modelo, se realiza la reacción de macrociclación catalizada por clústeres de paladio en disolución, y se obtienen los macrociclos con buenos rendimientos en una concentración de hasta 1M. También se han realizado estudios mecanísticos tanto computacionales como cinéticos. Por último, se ha realizado la síntesis de dos fosfinas voluminosas basadas en una fragancia, y su posterior estudio de coordinación con el paladio y su alcance catalítico en reacciones orgánicas de interés, como son la telomerización de isopreno, y las reacciones de acoplamiento Buchwald-Hartwig y Suzuki con cloroderivados, donde se comprueba la capacidad catalítica de los complejos formados con nuestras fosfinas y el paladio. / [CA] En la present tesi doctoral s'ha dut a terme un estudi de noves reaccions orgàniques d'interés catalitzades per diferents espècies de pal·ladi, tant clústers com complexos metàl·lics. En primer lloc, s'ha estudiat la reacció intramolecular regioirregular de Mizoroki- Heck catalitzada per clústers de pal·ladi en dissolució, on s'han posat en contrast les propietats electròniques i estèriques de la reacció de Mizoroki-Heck obtenint la reacció de ciclació amb una regioselectivitat inversa. També s'han realitzat estudis mecanístics mitjançant estudis cinètics i computacionals. També s'ha desenvolupat un catalitzador sòlid basat en zeolita, concretament la zeolita X, que després de fer-li intercanvi de cations i introduir el Pd que catalitza la reacció a l'interior, s'ha aconseguit obtindre un centre actiu amb les condicions tant estèriques com electròniques òptimes per a realitzar la reacció intermolecular regioirregular de Mizoroki-Heck entre estirens i iodobencenos amb bons rendiments i selectivitats. D'altra banda, s'ha estudiat una nova ruta de síntesi d'una fragància comercial, la deshidromuscona, on s'obté un rendiment global de síntesi major que l'obtingut actualment en la indústria, tot això en un menor nombre de passos, on s'ha dut a terme un estudi més intens d'un pas on es realitza una macrociclació en alta concentració per a poder ser viable industrialment. Mitjançant la reacció de Mizoroki-Heck estudiada anteriorment, s'ha dut a terme un estudi de macrociclació en alta concentració on a partir uns substrats model es realitza la reacció de macrociclació catalitzada per clústers de pal·ladi en dissolució on s'obtenen els macrocicles amb bons rendiments en una concentració fins del 1M. També s'han realitzat estudis mecanístics tant computacionals com cinètics. Finalment, s'ha realitzat la síntesi de dues fosfines voluminoses basades en fragàncies i el seu posterior estudi de coordinació amb el pal·ladi i el seu abast catalític en reaccions orgàniques difícils, com són la telomerización, la Buchwald-Hartwig o la Suzuki, comprovant la capacitat catalítica dels complexos formats amb les nostres fosfines i el pal·ladi. / [EN] In this doctoral thesis, a study of new organic reactions of interest catalyzed by different palladium species, both clusters and metal complexes, has been carried out. Firstly, the intramolecular regioirregular Mizoroki-Heck reaction catalyzed by palladium clusters in solution has been studied, where the electronic and steric properties of the Mizoroki-Heck reaction have been contrasted, obtaining the cyclization reaction with an inverse regioselectivity. Mechanistic studies have also been carried out by kinetic and computational studies. A solid catalyst based on a zeolite has also been developed, specifically zeolite X, which after making cation exchange and introducing the Pd that catalyzes the reaction inside, it has been possible to obtain an active center with the optimum steric and electronic conditions to carry out the intermolecular regioirregular Mizoroki-Heck reaction between styrenes and iodobenzenes, with good yields and selectivities. On the other hand, a new route for the synthesis of a commercial fragrance, dehydromuscone, has been studied, where a higher overall synthesis yield than the one currently obtained in the industry is obtained. The new synthesis is carried out in less number steps, and a more intense study on the macrocyclization reactive in high concentration has been carried out, in order to evaluate if it is industrially viable. By means of the Mizoroki-Heck reaction studied previously, a study of macrocyclization at high concentration has been carried out where, from some model substrates, the macrocyclization reaction catalyzed by palladium clusters in solution is carried out, to obtain macrocycles with good yields and in a concentration up to 1M. Both computational and kinetic mechanistic studies have also been performed. Finally, the synthesis of two bulky phosphines based on a commercial fragrance and their subsequent coordination with palladium has been studied. Their catalytic scope in challenging organic reactions, such as the telomerization of isoprene, and the Buchwald-Hartwig and Suzuki cross-coupling reactions of chloroderivatives, have been carried out, verifying the catalytic capacity of the complexes formed with our phosphines and palladium. / Garnes Pórtoles, F. (2023). Nuevas reacciones de acoplamiento cruzado de alquenos terminales altamente regioselectivas y catalizadas por paladio [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/195109

CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / Os resultados apresentados neste trabalho envolvem a sÃntese de compostos de coordenaÃÃo contendo fosfinas e ligantes redox ativos (ligantes nÃo-inocentes) na esfera de coordenaÃÃo do rutÃnio. Este trabalho està inserido em uma linha de pesquisa do Grupo de BioinorgÃnica que visa, como objetivo final, a aplicaÃÃo dos compostos isolados na catÃlise de reaÃÃes de hidrogenaÃÃo. Durante o desenvolvimento das atividades de doutorado, perÃodo de marÃo de 2010 a janeiro de 2015, foram sintetizados seis (06) compostos inÃditos na literatura, um dos quais sendo classificado como complexo precursor, [RuIICl2(binap)(PPh3)], onde binap = 2,2′-bis(difenilfosfina)-1,1′-dinaftaleno. Todos estes compostos foram caracterizados por ressonÃncia magnÃtica nuclear de fÃsforo (RMN 31P{1H}), anÃlise elementar e espectroscopias vibracional na regiÃo do infravermelho e eletrÃnica nas regiÃes do ultravioleta e visÃvel. A despeito das diversas tentativas de formaÃÃo de cristais dos complexos isolados, apenas o composto trans-[RuIICl2(dppb)(opda-Clcat)], onde dppb = 1,4-bis(difenilfosfina)butano e opda-Clcat = 4-cloro-1,2-fenilenodiamina, forneceu cristais passÃveis de anÃlise por difraÃÃo de raios X. A partir dos resultados obtidos durante o perÃodo citado, dois trabalhos foram publicados em periÃdicos indexados (Polyhedron 2010, 29, 3349â3354 e Polyhedron 2012, 31, 104â109) e cinco trabalhos foram apresentados em congressos nacionais e internacionais. Os espectros de RMN 31P{1H} dos compostos sintetizados apresentaram um Ãnico sinal indicando que os Ãtomos de fÃsforo ocupam posiÃÃes equivalentes e trans aos Ãtomos doadores dos ligantes nÃo-inocentes. Apenas o composto trans-[RuIICl2(dppb)(opda-Clcat)] apresentou um dubleto de dubleto que foi atribuÃdo à assimetria do ligante opda-Cl, sendo confirmado pelos dados de difraÃÃo de raios X. Os dados de espectroscopia eletrÃnica indicaram o estado oxidado dos ligantes o-fenilÃnicos apÃs coordenaÃÃo ao centro metÃlico sendo possÃvel, portanto, a observaÃÃo de interaÃÃes de retrodoaÃÃo. Os ensaios de atividade catalÃtica foram monitorados por cromatografia gasosa acoplada à espectrometria de massa utilizando a reaÃÃo padrÃo de hidrogenaÃÃo da molÃcula de acetofenona ao Ãlcool 1-feniletanol. AlÃm dos complexos originalmente apresentados nesta tese, [RuIICl2(binap)(PPh3)](1), trans-[RuIICl2(binap)(opda-Clcat)](2), trans-[RuIICl2(binap)(fenantq)](3), trans-[RuIICl2(PPh3)2(opdaq)](5) e trans-[RuIICl2(PPh3)2(fenantq)](6), onde fenantq e opdaq sÃo, respectivamente, 9,10-fenantrequinona e 1,2-fenilenodiamina, tais ensaios foram, tambÃm, realizados com compostos previamente sintetizados durante a dissertaÃÃo de mestrado e por outros membros do Grupo de BioinorgÃnica, resultando em um total de vinte (20) catalisadores estudados. Destes complexos, dois foram estudados em condiÃÃes heterogÃneas apÃs imobilizaÃÃo sobre esferas hÃbridas de sÃlica/quitosana. Dentre os sistemas estudados, os complexos trans-[RuIICl2(dppb)(Quinone)](10), cis-[RuIICl2(dppb)(opda-Clq)](13), trans-[RuIICl2(dppb)(tabq,cat)](15) e cis-[RuIICl2(dppb)(tabq,cat)](16), onde tabq,cat = 3,3â,4,4â-tetraaminobifenil, apresentaram os mais altos valores de conversÃo (> 90%) em todas as condiÃÃes analisadas. Os valores de conversÃo observados para os sistemas heterogÃneos, ~ 60%, embora menores que aqueles calculados para os sistemas homogÃneos em condiÃÃes similares, nÃo representam desvantagem, uma vez que implicam na reduÃÃo da etapa de separaÃÃo. Os compostos que apresentaram maiores valores de conversÃo em meio homogÃneo apresentam, em comum, a presenÃa de ligantes nÃo-inocentes no estado oxidado. Essa observaÃÃo indica a presenÃa de efeitos sinÃrgicos que influenciam na afinidade do substrato, a citar: (i) aumento da acidez de Lewis do metal pela oxidaÃÃo do ligante e (ii) funÃÃo de reservatÃrio de densidade eletrÃnica do ligante redox ativo que permitir o metal estocar (doar) densidade eletrÃnica no (para o) ligante durante as etapas elementares do ciclo catalÃtico, evitando a localizaÃÃo excessiva de carga sobre o metal. / The results presented in this thesis involve the synthesis of coordination compounds containing phosphine ligands and redox active (non-innocent ligands) in the ruthenium coordination sphere. This work is part of a research line of Bioinorganic Group research aimed, as the ultimate goal, the application of the isolated compounds in catalysis of hydrogenation reactions. During the development of PhD activities, from March 2010 to January 2015, six compounds (06) unpublished in the literature were synthesized; one of which being classified as a precursor complex, [RuIICl2(binap)(PPh3)], where binap = 2,2′-bis(diphenylphosphine)-1,1′-dinaphthalene. All of these complexes were characterized by means of phosphorous nuclear resonance magnetic (RMN 31P{1H}), elemental analysis, infrared spectroscopy and electronic spectroscopy in the ultraviolet and visible regions. Despite several attempts to produce crystals of the synthesized compounds, only the trans-[RuIICl2(dppb)(opda-Clcat)] complex, where dppb = 1,4-bis(diphenylphosphine)butane and opda-Clcat = 4-cloro-1,2-phenylenediamine, yielded suitable crystals for determination of X-ray structure. From the results obtained during the cited time, two papers were published in indexed journals ((Polyhedron 2010, 29, 3349â3354 and Polyhedron 2012, 31, 104â109) and five works were shown in national and international meetings. The RMN 31P{1H} spectra of the isolated compounds presented only one signal indicating that the phosphorous atoms lie in equivalent positions and trans in relation to the donor atoms of the non-innocent ligands. For the trans-[RuIICl2(dppb)(opda-Clcat)] complex, however, a dublet of dublet was observed and was assigned to the assimetry of the opda-Cl moiety, which was confirmed by X ray diffraction. The electronic spectroscopic data indicated the oxidized state of the o-phenylene ligands upon coordination to the metal atom thus making possible the back-bonding interaction. The catalytic activity assays were monitored by gas chromatography coupled to mass spectrometry using the standard hydrogenation reaction of the alcohol molecule acetophenone to 1-phenyl ethanol. In addition to the complex originally presented in this thesis, [RuIICl2(binap)(PPh3)](1), trans-[RuIICl2(binap)(opda-Clcat)](2), trans-[RuIICl2(binap)(fenantq)](3), trans-[RuIICl2(PPh3)2(opdaq)](5) and trans-[RuIICl2(PPh3)2(fenantq)](6), where fenantq and opdaq are, respectively, 9,10-phenanthraquinone and 1,2-phenylenediamine, such assays were also carried out for compounds which were previously synthesized during the master course and by other researchers of the Bioinorganic Group resulting resulting in a total of twenty (20) studied catalysts. Among these complexes, two were studied in heterogeneous condition upon immobilization on hybrid spheres of silica chitosan. By accounting for all the studied conditions, the highest values of conversion (> 90%) were observed for trans-[RuIICl2(dppb)(Quinone)](10), cis-[RuIICl2(dppb)(opda-Clq)](13), trans-[RuIICl2(dppb)(tabq,cat)](15) and cis-[RuIICl2(dppb)(tabq,cat)](16), where tabq,cat = 3,3â,4,4â-tetraaminobiphenyls. The values of conversion observed for the heterogeneous systems, c.a. 60%, although lower than those calculated for the homogeneous systems under similar conditions, do not constitute a disadvantage, since separation step is no longer needed. The compounds that showed the higher conversion values in homogeneous medium feature in common the presence of non-innocent ligands in the oxidized state. This observation indicates, very probably, two synergistic effects which influence the affinity of the substrate: (i) the increase of the Lewis acidity of the metal by the oxidation of the ligand and (ii) the function of electron density reservoir of the redox active ligand that allows the metal to store (donate) electron density from (to) the ligand during the elementary steps of the catalytic cycle by preventing excessive charge density on the metal.