Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina
Ano de defesa: | 2018 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , |
Tipo de documento: | Dissertação |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
Centro de Ciências Naturais e Exatas |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
Brasil
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/16405 |
Resumo: | This work presents the synthesis and characterization of eight compounds derived from a new synthesis methodology of the 2-picolyl selonopyridine linker with metals of different hardness. All the compounds had their structure elucidated by X-ray diffraction in monocrystal, besides other characterization methods, such as infrared spectroscopy, elemental analysis and mass spectrometry. Six different complexes were obtained from the direct reaction of the ligand with metal salts, these complexes involving CuII, CuI, CoII and PdII ions. The other two complexes were obtained from the same reaction proposal, however during prolonged exposure to air, the oxidation of the ligand was observed. Among the eight compounds synthesized in this work, seven are inedited in the literature (1, 2, 2a, 2b, 3, 4 and 5). The aliphatic carbon present in the structure of the ligand under study acts as a spacer and was used to evaluate its influence on the complexation with transition metals of different hardness, in order to provide flexibility and greater stability to the complexes formed. All the compounds obtained in this work have been shown to follow a complexation trend that is in agreement with Pearson's theory of acids and bases, where hard bases such as nitrogen and oxygen atoms coordinate hard metals and soft acids like the selenium atom to metals soft. In one of the complexes obtained, compound 5 formed an organometallic with PdII, a proposed mechanism was performed in order to elucidate this behavior. Compound 1 was submitted to analysis of the behavior as a photosensitizer of TiO2 in photocatalysis tests in the production of hydrogen gas from the photolysis of the water using a simulator of sunlight. The composite 1 as it was denominated, presented satisfactory quantitative results in the evolution of H2 production, at its apex it was 79% more efficient than the commercially available comparative material, besides presenting a high optical band gap of 3.53 eV. |
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2019-05-07T12:24:13Z2019-05-07T12:24:13Z2018-10-29http://repositorio.ufsm.br/handle/1/16405This work presents the synthesis and characterization of eight compounds derived from a new synthesis methodology of the 2-picolyl selonopyridine linker with metals of different hardness. All the compounds had their structure elucidated by X-ray diffraction in monocrystal, besides other characterization methods, such as infrared spectroscopy, elemental analysis and mass spectrometry. Six different complexes were obtained from the direct reaction of the ligand with metal salts, these complexes involving CuII, CuI, CoII and PdII ions. The other two complexes were obtained from the same reaction proposal, however during prolonged exposure to air, the oxidation of the ligand was observed. Among the eight compounds synthesized in this work, seven are inedited in the literature (1, 2, 2a, 2b, 3, 4 and 5). The aliphatic carbon present in the structure of the ligand under study acts as a spacer and was used to evaluate its influence on the complexation with transition metals of different hardness, in order to provide flexibility and greater stability to the complexes formed. All the compounds obtained in this work have been shown to follow a complexation trend that is in agreement with Pearson's theory of acids and bases, where hard bases such as nitrogen and oxygen atoms coordinate hard metals and soft acids like the selenium atom to metals soft. In one of the complexes obtained, compound 5 formed an organometallic with PdII, a proposed mechanism was performed in order to elucidate this behavior. Compound 1 was submitted to analysis of the behavior as a photosensitizer of TiO2 in photocatalysis tests in the production of hydrogen gas from the photolysis of the water using a simulator of sunlight. The composite 1 as it was denominated, presented satisfactory quantitative results in the evolution of H2 production, at its apex it was 79% more efficient than the commercially available comparative material, besides presenting a high optical band gap of 3.53 eV.Este trabalho apresenta a síntese e a caracterização de oito compostos derivados de uma nova metodologia de síntese do ligante 2-(2-piridilselanometil)piridina com metais de diferente dureza. Todos os compostos tiveram sua estrutura elucidada por difração de raios X em monocristal, além de outros métodos de caracterização, como espectroscopia de infravermelho, análise elementar e espectrometria de massas. Seis diferentes complexos foram obtidos a partir da reação direta do ligante com sais metálicos, estes complexos envolvendo íons CuII, CuI, CoII e PdII. Os outros dois complexos foram obtidos a partir de uma mesma proposta reacional, entretanto durante a exposição prolongada ao ar, observou-se a oxidação do ligante. Dentre os oito compostos sintetizados nesse trabalho, sete são inétidos na literatura (1, 2, 2a, 2b, 3, 4 e 5). O carbono alifático presente na estrutura do ligante em estudo atua como espaçador e, foi utilizado com objetivo de avaliar sua influência frente a complexação com metais de transição de diferente dureza, com intuito de proporcionar flexibilidade e uma maior estabilidade aos complexos formados. Todos os compostos obtidos nesse trabalho demonstraram seguir uma tendência de complexação que está de acordo com a teoria de Pearson sobre ácidos e bases, onde bases duras como átomos de nitrogênio e oxigênio coordenam a metais duros e ácidos macios como o átomo de selênio a metais mais macios. O composto 5 formou-se um organometálico com PdII, uma proposta de mecanismo foi realizada a fim de elucidar esse comportamento. O composto 1 foi submetido a análise do comportamento como fotosensibilizador do TiO2 em testes de fotocatálise na produção de gás hidrogênio a partir da fotólise da água utilizando um simulador de luz solar. O compósito 1 como foi denominado, apresentou resultados satisfatórios em termos quantitativos na evolução da produção de H2, em seu ápice mostrou-se 79% mais eficiente do que o material comparativo disponível comercialmente, além de apresentar band gap ótico elevado de 3,53 eV.porUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccess2-(2-piridilselanometil)piridinaComplexos metálicosFotocatálise2-picolyl selenopyridineMetal complexesPhotocatalysisCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridinaSyntheis and structural chmistry of (CoII, CuII, CuI, PdII ) complexes containing 2-picolyl selenopyridine as a ligandinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisLang, Ernesto Schulzhttp://lattes.cnpq.br/4481982189769819Vicenti, Juliano Rosa de Menezeshttp://lattes.cnpq.br/8692948387211118Tirloni, Bárbarahttp://lattes.cnpq.br/2866324870100182http://lattes.cnpq.br/5264899199232856Delgado, Cássia Pereira1006000000006000c9d7568-d5c4-466d-b807-0125a7d37b97a739c5b5-5f10-4c56-9120-47012c5f4a238e9b0c9e-0828-46c2-81b6-648195273f36c1e37583-819e-4d38-bfe8-27059d8abef6reponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALDIS_PPGQUIMICA_2018_DELGADO_CASSIA.pdfDIS_PPGQUIMICA_2018_DELGADO_CASSIA.pdfDissertação de Mestradoapplication/pdf5188321http://repositorio.ufsm.br/bitstream/1/16405/1/DIS_PPGQUIMICA_2018_DELGADO_CASSIA.pdf0b2f408f88be9f0ca63c93d251fb70feMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv |
Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina |
dc.title.alternative.eng.fl_str_mv |
Syntheis and structural chmistry of (CoII, CuII, CuI, PdII ) complexes containing 2-picolyl selenopyridine as a ligand |
title |
Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina |
spellingShingle |
Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina Delgado, Cássia Pereira 2-(2-piridilselanometil)piridina Complexos metálicos Fotocatálise 2-picolyl selenopyridine Metal complexes Photocatalysis CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina |
title_full |
Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina |
title_fullStr |
Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina |
title_full_unstemmed |
Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina |
title_sort |
Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina |
author |
Delgado, Cássia Pereira |
author_facet |
Delgado, Cássia Pereira |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Lang, Ernesto Schulz |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/4481982189769819 |
dc.contributor.referee1.fl_str_mv |
Vicenti, Juliano Rosa de Menezes |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/8692948387211118 |
dc.contributor.referee2.fl_str_mv |
Tirloni, Bárbara |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/2866324870100182 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/5264899199232856 |
dc.contributor.author.fl_str_mv |
Delgado, Cássia Pereira |
contributor_str_mv |
Lang, Ernesto Schulz Vicenti, Juliano Rosa de Menezes Tirloni, Bárbara |
dc.subject.por.fl_str_mv |
2-(2-piridilselanometil)piridina Complexos metálicos Fotocatálise |
topic |
2-(2-piridilselanometil)piridina Complexos metálicos Fotocatálise 2-picolyl selenopyridine Metal complexes Photocatalysis CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
2-picolyl selenopyridine Metal complexes Photocatalysis |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work presents the synthesis and characterization of eight compounds derived from a new synthesis methodology of the 2-picolyl selonopyridine linker with metals of different hardness. All the compounds had their structure elucidated by X-ray diffraction in monocrystal, besides other characterization methods, such as infrared spectroscopy, elemental analysis and mass spectrometry. Six different complexes were obtained from the direct reaction of the ligand with metal salts, these complexes involving CuII, CuI, CoII and PdII ions. The other two complexes were obtained from the same reaction proposal, however during prolonged exposure to air, the oxidation of the ligand was observed. Among the eight compounds synthesized in this work, seven are inedited in the literature (1, 2, 2a, 2b, 3, 4 and 5). The aliphatic carbon present in the structure of the ligand under study acts as a spacer and was used to evaluate its influence on the complexation with transition metals of different hardness, in order to provide flexibility and greater stability to the complexes formed. All the compounds obtained in this work have been shown to follow a complexation trend that is in agreement with Pearson's theory of acids and bases, where hard bases such as nitrogen and oxygen atoms coordinate hard metals and soft acids like the selenium atom to metals soft. In one of the complexes obtained, compound 5 formed an organometallic with PdII, a proposed mechanism was performed in order to elucidate this behavior. Compound 1 was submitted to analysis of the behavior as a photosensitizer of TiO2 in photocatalysis tests in the production of hydrogen gas from the photolysis of the water using a simulator of sunlight. The composite 1 as it was denominated, presented satisfactory quantitative results in the evolution of H2 production, at its apex it was 79% more efficient than the commercially available comparative material, besides presenting a high optical band gap of 3.53 eV. |
publishDate |
2018 |
dc.date.issued.fl_str_mv |
2018-10-29 |
dc.date.accessioned.fl_str_mv |
2019-05-07T12:24:13Z |
dc.date.available.fl_str_mv |
2019-05-07T12:24:13Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
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masterThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/16405 |
url |
http://repositorio.ufsm.br/handle/1/16405 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 |
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dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
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