Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina

Detalhes bibliográficos
Ano de defesa: 2018
Autor(a) principal: Delgado, Cássia Pereira lattes
Orientador(a): Lang, Ernesto Schulz lattes
Banca de defesa: Vicenti, Juliano Rosa de Menezes lattes, Tirloni, Bárbara lattes
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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spelling 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
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dc.identifier.uri.fl_str_mv http://repositorio.ufsm.br/handle/1/16405
url http://repositorio.ufsm.br/handle/1/16405
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dc.rights.driver.fl_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
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rights_invalid_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
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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
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