Compostos de coordenação derivados do disseleneto e disselenoéteres de bis(2-piridina) síntese, caracterização e aplicações
Ano de defesa: | 2015 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , , |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
|
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
BR
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/4267 |
Resumo: | This work describes the synthesis and characterization of nineteen compounds derivative of diselenide and diselenoethers of bis(2-pyridyl) with metals of different degree of hardness. Among the nineteen obtained complex, seventeen had their structure elucidated by X-ray crystallography, besides others characterization methods, such as elemental analysis, infrared spectroscopy and mass spectrometry. Six different complexes were obtained when bis(2-pyridyl)diselenide was used as a ligand. These complexes involve metal centers of AuI, CuII, CuI, ReI, ReV and ReIII. Among the rhenium complexes, stands out the ReV complex that has a Se0 atom as a ligand, a rare exemple not previously reported in the literature. Bis(2-pyridyl)diselenoethers with one, three or four methylene groups between selenium atoms were synthesized and characterized. Among these three synthesized diselenoethers two are unprecedented in the literature (L2, L3). The methylene groups act as spacers, and were used in order to evaluate their influence across the complexation with different metals. It was observed that as longer is the carbon chain between the selenium atoms as higher is the tendency to polymer formation. The thirteen complexes obtained with the ligands bis(2-pyridyl)diselenoethers demonstrated follow a trend of complexation which agrees with Pearson's theory of acids and bases, wherein the nitrogen atoms of the ligands coordinate with harder metals and selenium atoms coordinate the softer metals. The obtained complexes were submitted to antioxidant activity tests. Tests of superoxide dismutase (SOD) showed that copper complexes 2, 7, 8, 13 and 18 had good antioxidant activity, with IC50 values less than 0.66 μM. Among these compounds the complex [Cu4I4(L1)2] (8) presented the best IC50 value in 0.08 μM. These results demonstrate that the Cu compounds mentioned have great potential to be used as mimetics of superoxide dismutase enzyme (SOD). In addition, the system CuI/bis(2-pyridyl)diselenoether showed as an efficient catalyst for the formation of a new C-S bond by cross-coupling reactions using glycerol as solvent. Still, the catalytic activity for the complex 8 was also tested for this type of reaction. Both of these catalytic systems provide the desired products in good to excellent yields when compared to the literature. |
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2017-05-222017-05-222015-03-06CARGNELUTTI, Roberta. Coordination compounds derivatives of bis(2-piridyl) diselenide and diselenoethers synthesis, characterization and applications. 2015. 209 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2015.http://repositorio.ufsm.br/handle/1/4267This work describes the synthesis and characterization of nineteen compounds derivative of diselenide and diselenoethers of bis(2-pyridyl) with metals of different degree of hardness. Among the nineteen obtained complex, seventeen had their structure elucidated by X-ray crystallography, besides others characterization methods, such as elemental analysis, infrared spectroscopy and mass spectrometry. Six different complexes were obtained when bis(2-pyridyl)diselenide was used as a ligand. These complexes involve metal centers of AuI, CuII, CuI, ReI, ReV and ReIII. Among the rhenium complexes, stands out the ReV complex that has a Se0 atom as a ligand, a rare exemple not previously reported in the literature. Bis(2-pyridyl)diselenoethers with one, three or four methylene groups between selenium atoms were synthesized and characterized. Among these three synthesized diselenoethers two are unprecedented in the literature (L2, L3). The methylene groups act as spacers, and were used in order to evaluate their influence across the complexation with different metals. It was observed that as longer is the carbon chain between the selenium atoms as higher is the tendency to polymer formation. The thirteen complexes obtained with the ligands bis(2-pyridyl)diselenoethers demonstrated follow a trend of complexation which agrees with Pearson's theory of acids and bases, wherein the nitrogen atoms of the ligands coordinate with harder metals and selenium atoms coordinate the softer metals. The obtained complexes were submitted to antioxidant activity tests. Tests of superoxide dismutase (SOD) showed that copper complexes 2, 7, 8, 13 and 18 had good antioxidant activity, with IC50 values less than 0.66 μM. Among these compounds the complex [Cu4I4(L1)2] (8) presented the best IC50 value in 0.08 μM. These results demonstrate that the Cu compounds mentioned have great potential to be used as mimetics of superoxide dismutase enzyme (SOD). In addition, the system CuI/bis(2-pyridyl)diselenoether showed as an efficient catalyst for the formation of a new C-S bond by cross-coupling reactions using glycerol as solvent. Still, the catalytic activity for the complex 8 was also tested for this type of reaction. Both of these catalytic systems provide the desired products in good to excellent yields when compared to the literature.Este trabalho apresenta a síntese e caracterização de dezenove compostos derivados do disseleneto e disselenoéteres de bis(2-piridina) com metais de diferente dureza. Dos dezenove complexos obtidos, dezessete tiveram sua estrutura elucidada por difração de raios X em monocristal, além de outros métodos de caracterização como análise elementar, espectroscopia de infravermelho e espectrometria de massas. Seis diferentes complexos foram obtidos quando utilizou-se o disseleneto de bis(2-piridina) como ligante. Estes complexos envolvem os íons AuI, CuII, CuI, ReI, ReV e ReIII. Dentre os complexos de rênio, destaca-se o complexo de ReV que possui um átomo de Se0 como ligante, um caso raro até então não reportado na literatura. Disselenoéteres de bis(2-piridina) com um, três ou quatro carbonos metilênicos entre os átomos de selênio foram sintetizados e caracterizados. Dos três disselenoéteres sintetizados, dois são inéditos na literatura (L2, L3). Os grupos metilênicos atuam como espaçadores e foram utilizados com o objetivo de avaliar a sua influência frente à complexação com metais de transição de diferente dureza. Observou-se que quanto maior a cadeia carbônica entre os átomos de selênio maior é a tendência para a formação de polímeros. Os treze complexos obtidos com ligantes disselenoéteres de bis(2-piridina) demostraram seguir uma tendência de complexação que está de acordo com a teoria de Pearson sobre ácidos e bases, no qual os átomos de nitrogênio dos ligantes se coordenam a metais mais duros e os átomos de selênio se coordenam a metais mais macios. Os complexos obtidos foram submetidos a testes de atividade antioxidante. Os testes da atividade superóxido dismutase (SOD) demonstraram que os compostos de Cu 2, 7, 8, 13 e 18 apresentaram boa atividade antioxidante, com valores de IC50 menores que 0,66 μM. Dentre esses compostos o complexo [Cu4I4(L1)2] (8) foi o que apresentou o melhor valor de IC50 em 0,08 μM. Esses resultados demonstram que os compostos de Cu citados apresentam bons potenciais para serem empregados como miméticos da enzima superóxido dismutase (SOD). Adicionalmente, o sistema CuI/disselenoéter de bis(2-piridina) mostrou-se eficiente na catálise de reações de acoplamento para a formação de uma nova ligação C-S utilizando glicerol como solvente. Também testou-se a atividade catalítica do complexo 8 para este tipo de reação. Ambos os sistemas catalíticos deram origem a produtos com rendimentos de bons a excelentes quando comparados ao reportado na literatura.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaDisseleneto de bis(2-piridina)Disselenoéter de bis(2-piridina)ComplexosDifração de raios XBis(2-piridyl)diselenideBis(2-pyridyl)diselenoetherComplexesX-ray crystallographyCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICACompostos de coordenação derivados do disseleneto e disselenoéteres de bis(2-piridina) síntese, caracterização e aplicaçõesCoordination compounds derivatives of bis(2-piridyl) diselenide and diselenoethers synthesis, characterization and applicationsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisLang, Ernesto Schulzhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4786424E6Giacomelli, Cristianohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4762951A6Gregório, José Ribeirohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782325T6Lanznaster, Mauriciohttp://lattes.cnpq.br/5123336948991939Rodrigues, Oscar Endrigo Dorneleshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4763956Z6http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4276823U9Cargnelutti, Roberta1006000000004003003003003003005000c9d7568-d5c4-466d-b807-0125a7d37b97c92c205c-9b61-46d9-8e18-01e9e951d3ba76f4b1a0-03ef-48e6-88aa-6c682d7ea2f4b4da48ea-85f3-4273-8cfd-d547fc352a5da8e5568e-7ead-4655-bd47-090c426e963b9dfccbe0-bd16-4e23-a1fb-8e55f871ce46info:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALCARGNELUTTI, ROBERTA.pdfapplication/pdf10328104http://repositorio.ufsm.br/bitstream/1/4267/1/CARGNELUTTI%2c%20ROBERTA.pdfd0fff3315c29e16428c137ba2625b277MD51TEXTCARGNELUTTI, ROBERTA.pdf.txtCARGNELUTTI, ROBERTA.pdf.txtExtracted texttext/plain246912http://repositorio.ufsm.br/bitstream/1/4267/2/CARGNELUTTI%2c%20ROBERTA.pdf.txta640ad1542bc3bab8a184eb7497eed44MD52THUMBNAILCARGNELUTTI, ROBERTA.pdf.jpgCARGNELUTTI, ROBERTA.pdf.jpgIM Thumbnailimage/jpeg4604http://repositorio.ufsm.br/bitstream/1/4267/3/CARGNELUTTI%2c%20ROBERTA.pdf.jpgec5998e513f9c5938ca13eab3bb8717bMD531/42672017-07-25 11:05:06.987oai:repositorio.ufsm.br:1/4267Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2017-07-25T14:05:06Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Compostos de coordenação derivados do disseleneto e disselenoéteres de bis(2-piridina) síntese, caracterização e aplicações |
dc.title.alternative.eng.fl_str_mv |
Coordination compounds derivatives of bis(2-piridyl) diselenide and diselenoethers synthesis, characterization and applications |
title |
Compostos de coordenação derivados do disseleneto e disselenoéteres de bis(2-piridina) síntese, caracterização e aplicações |
spellingShingle |
Compostos de coordenação derivados do disseleneto e disselenoéteres de bis(2-piridina) síntese, caracterização e aplicações Cargnelutti, Roberta Disseleneto de bis(2-piridina) Disselenoéter de bis(2-piridina) Complexos Difração de raios X Bis(2-piridyl)diselenide Bis(2-pyridyl)diselenoether Complexes X-ray crystallography CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Compostos de coordenação derivados do disseleneto e disselenoéteres de bis(2-piridina) síntese, caracterização e aplicações |
title_full |
Compostos de coordenação derivados do disseleneto e disselenoéteres de bis(2-piridina) síntese, caracterização e aplicações |
title_fullStr |
Compostos de coordenação derivados do disseleneto e disselenoéteres de bis(2-piridina) síntese, caracterização e aplicações |
title_full_unstemmed |
Compostos de coordenação derivados do disseleneto e disselenoéteres de bis(2-piridina) síntese, caracterização e aplicações |
title_sort |
Compostos de coordenação derivados do disseleneto e disselenoéteres de bis(2-piridina) síntese, caracterização e aplicações |
author |
Cargnelutti, Roberta |
author_facet |
Cargnelutti, Roberta |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Lang, Ernesto Schulz |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4786424E6 |
dc.contributor.referee1.fl_str_mv |
Giacomelli, Cristiano |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4762951A6 |
dc.contributor.referee2.fl_str_mv |
Gregório, José Ribeiro |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782325T6 |
dc.contributor.referee3.fl_str_mv |
Lanznaster, Mauricio |
dc.contributor.referee3Lattes.fl_str_mv |
http://lattes.cnpq.br/5123336948991939 |
dc.contributor.referee4.fl_str_mv |
Rodrigues, Oscar Endrigo Dorneles |
dc.contributor.referee4Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4763956Z6 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4276823U9 |
dc.contributor.author.fl_str_mv |
Cargnelutti, Roberta |
contributor_str_mv |
Lang, Ernesto Schulz Giacomelli, Cristiano Gregório, José Ribeiro Lanznaster, Mauricio Rodrigues, Oscar Endrigo Dorneles |
dc.subject.por.fl_str_mv |
Disseleneto de bis(2-piridina) Disselenoéter de bis(2-piridina) Complexos Difração de raios X |
topic |
Disseleneto de bis(2-piridina) Disselenoéter de bis(2-piridina) Complexos Difração de raios X Bis(2-piridyl)diselenide Bis(2-pyridyl)diselenoether Complexes X-ray crystallography CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Bis(2-piridyl)diselenide Bis(2-pyridyl)diselenoether Complexes X-ray crystallography |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work describes the synthesis and characterization of nineteen compounds derivative of diselenide and diselenoethers of bis(2-pyridyl) with metals of different degree of hardness. Among the nineteen obtained complex, seventeen had their structure elucidated by X-ray crystallography, besides others characterization methods, such as elemental analysis, infrared spectroscopy and mass spectrometry. Six different complexes were obtained when bis(2-pyridyl)diselenide was used as a ligand. These complexes involve metal centers of AuI, CuII, CuI, ReI, ReV and ReIII. Among the rhenium complexes, stands out the ReV complex that has a Se0 atom as a ligand, a rare exemple not previously reported in the literature. Bis(2-pyridyl)diselenoethers with one, three or four methylene groups between selenium atoms were synthesized and characterized. Among these three synthesized diselenoethers two are unprecedented in the literature (L2, L3). The methylene groups act as spacers, and were used in order to evaluate their influence across the complexation with different metals. It was observed that as longer is the carbon chain between the selenium atoms as higher is the tendency to polymer formation. The thirteen complexes obtained with the ligands bis(2-pyridyl)diselenoethers demonstrated follow a trend of complexation which agrees with Pearson's theory of acids and bases, wherein the nitrogen atoms of the ligands coordinate with harder metals and selenium atoms coordinate the softer metals. The obtained complexes were submitted to antioxidant activity tests. Tests of superoxide dismutase (SOD) showed that copper complexes 2, 7, 8, 13 and 18 had good antioxidant activity, with IC50 values less than 0.66 μM. Among these compounds the complex [Cu4I4(L1)2] (8) presented the best IC50 value in 0.08 μM. These results demonstrate that the Cu compounds mentioned have great potential to be used as mimetics of superoxide dismutase enzyme (SOD). In addition, the system CuI/bis(2-pyridyl)diselenoether showed as an efficient catalyst for the formation of a new C-S bond by cross-coupling reactions using glycerol as solvent. Still, the catalytic activity for the complex 8 was also tested for this type of reaction. Both of these catalytic systems provide the desired products in good to excellent yields when compared to the literature. |
publishDate |
2015 |
dc.date.issued.fl_str_mv |
2015-03-06 |
dc.date.accessioned.fl_str_mv |
2017-05-22 |
dc.date.available.fl_str_mv |
2017-05-22 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
CARGNELUTTI, Roberta. Coordination compounds derivatives of bis(2-piridyl) diselenide and diselenoethers synthesis, characterization and applications. 2015. 209 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2015. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4267 |
identifier_str_mv |
CARGNELUTTI, Roberta. Coordination compounds derivatives of bis(2-piridyl) diselenide and diselenoethers synthesis, characterization and applications. 2015. 209 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2015. |
url |
http://repositorio.ufsm.br/handle/1/4267 |
dc.language.iso.fl_str_mv |
por |
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por |
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100600000000 |
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400 300 300 300 300 300 500 |
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0c9d7568-d5c4-466d-b807-0125a7d37b97 c92c205c-9b61-46d9-8e18-01e9e951d3ba 76f4b1a0-03ef-48e6-88aa-6c682d7ea2f4 b4da48ea-85f3-4273-8cfd-d547fc352a5d a8e5568e-7ead-4655-bd47-090c426e963b 9dfccbe0-bd16-4e23-a1fb-8e55f871ce46 |
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openAccess |
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Universidade Federal de Santa Maria |
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Programa de Pós-Graduação em Química |
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UFSM |
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BR |
dc.publisher.department.fl_str_mv |
Química |
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Universidade Federal de Santa Maria |
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