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

Detalhes bibliográficos
Autor(a) principal: Delgado, Cássia Pereira
Data de Publicação: 2018
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Manancial - Repositório Digital da UFSM
dARK ID: ark:/26339/00130000168d2
Texto Completo: 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 Síntese 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 ligand2-(2-piridilselanometil)piridinaComplexos metálicosFotocatálise2-picolyl selenopyridineMetal complexesPhotocatalysisCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThis 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.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasLang, Ernesto Schulzhttp://lattes.cnpq.br/4481982189769819Vicenti, Juliano Rosa de Menezeshttp://lattes.cnpq.br/8692948387211118Tirloni, Bárbarahttp://lattes.cnpq.br/2866324870100182Delgado, Cássia Pereira2019-05-07T12:24:13Z2019-05-07T12:24:13Z2018-10-29info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/16405ark:/26339/00130000168d2porAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2019-05-08T06:02:05Zoai:repositorio.ufsm.br:1/16405Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2019-05-08T06:02:05Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false
dc.title.none.fl_str_mv Síntese e caracterização de complexos metálicos (CuI,CuII,CoII, PdII) derivados do ligante 2-(2-piridilselanometil)piridina
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.none.fl_str_mv Lang, Ernesto Schulz
http://lattes.cnpq.br/4481982189769819
Vicenti, Juliano Rosa de Menezes
http://lattes.cnpq.br/8692948387211118
Tirloni, Bárbara
http://lattes.cnpq.br/2866324870100182
dc.contributor.author.fl_str_mv Delgado, Cássia Pereira
dc.subject.por.fl_str_mv 2-(2-piridilselanometil)piridina
Complexos metálicos
Fotocatálise
2-picolyl selenopyridine
Metal complexes
Photocatalysis
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
topic 2-(2-piridilselanometil)piridina
Complexos metálicos
Fotocatálise
2-picolyl selenopyridine
Metal complexes
Photocatalysis
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.none.fl_str_mv 2018-10-29
2019-05-07T12:24:13Z
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
format masterThesis
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://repositorio.ufsm.br/handle/1/16405
dc.identifier.dark.fl_str_mv ark:/26339/00130000168d2
url http://repositorio.ufsm.br/handle/1/16405
identifier_str_mv ark:/26339/00130000168d2
dc.language.iso.fl_str_mv por
language por
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.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Universidade Federal de Santa Maria
Brasil
Química
UFSM
Programa de Pós-Graduação em Química
Centro de Ciências Naturais e Exatas
publisher.none.fl_str_mv Universidade Federal de Santa Maria
Brasil
Química
UFSM
Programa de Pós-Graduação em Química
Centro de Ciências Naturais e Exatas
dc.source.none.fl_str_mv reponame:Manancial - Repositório Digital da UFSM
instname:Universidade Federal de Santa Maria (UFSM)
instacron:UFSM
instname_str Universidade Federal de Santa Maria (UFSM)
instacron_str UFSM
institution UFSM
reponame_str Manancial - Repositório Digital da UFSM
collection Manancial - Repositório Digital da UFSM
repository.name.fl_str_mv Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)
repository.mail.fl_str_mv atendimento.sib@ufsm.br||tedebc@gmail.com
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