Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol

Detalhes bibliográficos
Ano de defesa: 2015
Autor(a) principal: Katayama, Juliana Midori Toia
Orientador(a): Dockal, Edward Ralph lattes
Banca de defesa: Não Informado pela instituição
Tipo de documento: Dissertação
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Universidade Federal de São Carlos
Câmpus São Carlos
Programa de Pós-Graduação: Programa de Pós-Graduação em Química - PPGQ
Departamento: Não Informado pela instituição
País: Não Informado pela instituição
Palavras-chave em Português:
Área do conhecimento CNPq:
Link de acesso: https://repositorio.ufscar.br/handle/20.500.14289/7470
Resumo: Ruthenium complexes are known as versatile electron-transfer and energy-transfer compounds. Due to these unique characteristics, ruthenium complexes exhibit a wide range of applications in various research areas such as artificial photosynthesis, photomolecular devices, biological probes, oxidation catalysts and organic synthesis. In the last two decades, salophen ligands and their complexes have received much attention, mainly because of their extensive applications in the fields of synthesis and catalysis. Thus, ruthenium(III) complexes with Schiff bases have several potential applications in the catalytic reactions such as cyclopropanation, epoxidation, aziridination, sulfimidation, catechols oxidation and Diels-Alder reactions. In this work were synthesized ligands and ruthenium complexes containing tridentate and tetradentate Schiff bases, which have substituted aromatic diimines, with satisfactory yields. The compounds synthesized in this work were characterized by melting point measurements, solubility tests, conductivity measurements, vibrational spectroscopy in the IR region, absorption spectra in the UV-vis, and cyclic voltammetry. The ligands were also characterized by nuclear magnetic resonance. The synthesized complex catalyzed oxidation of the substrate, 3,5-di-tert-butylcatechol, in their respective quinone; and these transformations were accompanied by absorption spectroscopy in the UV-vis region in 24 hours of reaction. The complexes’ structures have allowed structural and electronic effects to be evaluated and correlated with their catalytic activities. Although slow and low substrate conversion, less than 30%, trends were observed for correlations between structure and catalytic activity. The percentages of 3,5-di-tert-butilquinone obtained for the best catalysts among these complexes suggests that there is a step of forming a catalytically active species during the reaction time.
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spelling Katayama, Juliana Midori ToiaDockal, Edward Ralphhttp://lattes.cnpq.br/6461328124491559http://lattes.cnpq.br/9455477476400501acf2a8a1-763d-45d6-9350-4c7f942e9fe52016-09-26T20:46:54Z2016-09-26T20:46:54Z2015-09-09KATAYAMA, Juliana Midori Toia. Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol. 2015. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2015. Disponível em: https://repositorio.ufscar.br/handle/20.500.14289/7470.https://repositorio.ufscar.br/handle/20.500.14289/7470Ruthenium complexes are known as versatile electron-transfer and energy-transfer compounds. Due to these unique characteristics, ruthenium complexes exhibit a wide range of applications in various research areas such as artificial photosynthesis, photomolecular devices, biological probes, oxidation catalysts and organic synthesis. In the last two decades, salophen ligands and their complexes have received much attention, mainly because of their extensive applications in the fields of synthesis and catalysis. Thus, ruthenium(III) complexes with Schiff bases have several potential applications in the catalytic reactions such as cyclopropanation, epoxidation, aziridination, sulfimidation, catechols oxidation and Diels-Alder reactions. In this work were synthesized ligands and ruthenium complexes containing tridentate and tetradentate Schiff bases, which have substituted aromatic diimines, with satisfactory yields. The compounds synthesized in this work were characterized by melting point measurements, solubility tests, conductivity measurements, vibrational spectroscopy in the IR region, absorption spectra in the UV-vis, and cyclic voltammetry. The ligands were also characterized by nuclear magnetic resonance. The synthesized complex catalyzed oxidation of the substrate, 3,5-di-tert-butylcatechol, in their respective quinone; and these transformations were accompanied by absorption spectroscopy in the UV-vis region in 24 hours of reaction. The complexes’ structures have allowed structural and electronic effects to be evaluated and correlated with their catalytic activities. Although slow and low substrate conversion, less than 30%, trends were observed for correlations between structure and catalytic activity. The percentages of 3,5-di-tert-butilquinone obtained for the best catalysts among these complexes suggests that there is a step of forming a catalytically active species during the reaction time.Complexos de rutênio são conhecidos como compostos versáteis na transferência de elétrons e de energia. Devido a estas características únicas, complexos de rutênio apresentam uma vasta gama de aplicações em diversas áreas de pesquisa, como a fotossíntese artificial, dispositivos fotomoleculares, sondas biológicas, catalisadores de oxidação e síntese orgânica. Nas últimas duas décadas, os ligantes do tipo salophen e seus complexos têm recebido muita atenção, principalmente por causa de suas inúmeras aplicações nos domínios da síntese e catálise. Diante disso, complexos de rutênio(III) com bases de Schiff apresentam várias possibilidades de aplicações em reações catalíticas como: ciclopropanação, epoxidação, aziridinação, sulfimidação, oxidação de catecóis e reações Diels-Alder. Nesse trabalho foram sintetizados ligantes e complexos de rutênio contendo bases de Schiff tridentadas e tetradentadas, os quais apresentam diiminas aromáticas substituídas, com rendimentos satisfatórios. Esses compostos sintetizados foram caracterizados por ponto de fusão, solubilidade, medidas de condutividade, espectroscopia vibracional na região do IV, espectroscopia de absorção na região do UV-vis e voltametria cíclica; sendo que os ligantes também foram caracterizados por Ressonância Magnética Nuclear. Os complexos sintetizados catalisaram a oxidação do substrato, 3,5-di-terc-butilcatecol, em sua respectiva quinona; sendo essas transformações acompanhadas por espectroscopia de absorção da região do UV-vis em 24 horas de reação. As estruturas dos complexos permitiram que efeitos estruturais e eletrônicos pudessem ser avaliados e correlacionados com suas as atividades catalíticas. Apesar de lentas e das baixas conversões de substrato, inferiores a 30%, tendências foram constatadas por correlações entre estrutura e atividades catalíticas. As porcentagens de 3,5-di-tercbutilquinona obtidas para os melhores catalisadores dentre esses complexos sugere que há uma etapa de formação de uma espécie cataliticamente ativa durante o tempo reacional.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarQuímica inorgânicaComplexos de rutênioSchiff, Bases deOxidação de catecolCIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA::FISICO QUIMICA INORGANICAComplexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecolRuthenium (III) complexes with tridentate and tetradentate salophen type Schiff bases : Potential catalysts in the oxidation of catechol.info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisOnline600600c913d3d1-7fd3-4de7-aa1f-f7ada90c30f5info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALDissJMTK.pdfDissJMTK.pdfapplication/pdf2219272https://repositorio.ufscar.br/bitstreams/62a3e1dc-fb99-491d-bd0b-9f84b9fe0106/download9f24a292820e6aa9d2d9655ba3b87701MD51trueAnonymousREADLICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://repositorio.ufscar.br/bitstreams/8ed4e7fe-28b6-4c02-9fdc-d51fad32483a/downloadae0398b6f8b235e40ad82cba6c50031dMD52falseAnonymousREADTEXTDissJMTK.pdf.txtDissJMTK.pdf.txtExtracted texttext/plain162614https://repositorio.ufscar.br/bitstreams/63901df2-f35d-418d-b2b2-5d69bba87a1c/download14b73dce916ef55b4514c2dbfc8e5f47MD55falseAnonymousREADTHUMBNAILDissJMTK.pdf.jpgDissJMTK.pdf.jpgIM Thumbnailimage/jpeg7071https://repositorio.ufscar.br/bitstreams/71fb0f88-8f52-4aeb-a6bd-8cf0c0c813b5/download8fdfa11240290953f4937a6f2d05e88cMD56falseAnonymousREAD20.500.14289/74702025-02-05 17:15:11.763Acesso abertoopen.accessoai:repositorio.ufscar.br:20.500.14289/7470https://repositorio.ufscar.brRepositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestrepositorio.sibi@ufscar.bropendoar:43222025-02-05T20:15:11Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)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
dc.title.por.fl_str_mv Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol
dc.title.alternative.eng.fl_str_mv Ruthenium (III) complexes with tridentate and tetradentate salophen type Schiff bases : Potential catalysts in the oxidation of catechol.
title Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol
spellingShingle Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol
Katayama, Juliana Midori Toia
Química inorgânica
Complexos de rutênio
Schiff, Bases de
Oxidação de catecol
CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA::FISICO QUIMICA INORGANICA
title_short Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol
title_full Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol
title_fullStr Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol
title_full_unstemmed Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol
title_sort Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol
author Katayama, Juliana Midori Toia
author_facet Katayama, Juliana Midori Toia
author_role author
dc.contributor.authorlattes.por.fl_str_mv http://lattes.cnpq.br/9455477476400501
dc.contributor.author.fl_str_mv Katayama, Juliana Midori Toia
dc.contributor.advisor1.fl_str_mv Dockal, Edward Ralph
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/6461328124491559
dc.contributor.authorID.fl_str_mv acf2a8a1-763d-45d6-9350-4c7f942e9fe5
contributor_str_mv Dockal, Edward Ralph
dc.subject.por.fl_str_mv Química inorgânica
Complexos de rutênio
Schiff, Bases de
Oxidação de catecol
topic Química inorgânica
Complexos de rutênio
Schiff, Bases de
Oxidação de catecol
CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA::FISICO QUIMICA INORGANICA
dc.subject.cnpq.fl_str_mv CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA::FISICO QUIMICA INORGANICA
description Ruthenium complexes are known as versatile electron-transfer and energy-transfer compounds. Due to these unique characteristics, ruthenium complexes exhibit a wide range of applications in various research areas such as artificial photosynthesis, photomolecular devices, biological probes, oxidation catalysts and organic synthesis. In the last two decades, salophen ligands and their complexes have received much attention, mainly because of their extensive applications in the fields of synthesis and catalysis. Thus, ruthenium(III) complexes with Schiff bases have several potential applications in the catalytic reactions such as cyclopropanation, epoxidation, aziridination, sulfimidation, catechols oxidation and Diels-Alder reactions. In this work were synthesized ligands and ruthenium complexes containing tridentate and tetradentate Schiff bases, which have substituted aromatic diimines, with satisfactory yields. The compounds synthesized in this work were characterized by melting point measurements, solubility tests, conductivity measurements, vibrational spectroscopy in the IR region, absorption spectra in the UV-vis, and cyclic voltammetry. The ligands were also characterized by nuclear magnetic resonance. The synthesized complex catalyzed oxidation of the substrate, 3,5-di-tert-butylcatechol, in their respective quinone; and these transformations were accompanied by absorption spectroscopy in the UV-vis region in 24 hours of reaction. The complexes’ structures have allowed structural and electronic effects to be evaluated and correlated with their catalytic activities. Although slow and low substrate conversion, less than 30%, trends were observed for correlations between structure and catalytic activity. The percentages of 3,5-di-tert-butilquinone obtained for the best catalysts among these complexes suggests that there is a step of forming a catalytically active species during the reaction time.
publishDate 2015
dc.date.issued.fl_str_mv 2015-09-09
dc.date.accessioned.fl_str_mv 2016-09-26T20:46:54Z
dc.date.available.fl_str_mv 2016-09-26T20:46:54Z
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dc.identifier.citation.fl_str_mv KATAYAMA, Juliana Midori Toia. Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol. 2015. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2015. Disponível em: https://repositorio.ufscar.br/handle/20.500.14289/7470.
dc.identifier.uri.fl_str_mv https://repositorio.ufscar.br/handle/20.500.14289/7470
identifier_str_mv KATAYAMA, Juliana Midori Toia. Complexos de rutênio(III) com bases de Schiff tridentadas e tetradentadas do tipo Salophen : potenciais catalisadores na oxidação de catecol. 2015. Dissertação (Mestrado em Química) – Universidade Federal de São Carlos, São Carlos, 2015. Disponível em: https://repositorio.ufscar.br/handle/20.500.14289/7470.
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dc.publisher.none.fl_str_mv Universidade Federal de São Carlos
Câmpus São Carlos
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publisher.none.fl_str_mv Universidade Federal de São Carlos
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