Complexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculose
Autor(a) principal: | |
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Data de Publicação: | 2010 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/6503 |
Resumo: | In this work, a series of cis-[RuCl(L)(dppb)(5-mebipy)]PF6 (L=pyridine, 4- metylpyridine, 4-phenylpyridine, 4-vinylpyridine, 4-terc-butylpyridine and 4- aminopyridine); the cis-[RuCl(NO2)(dppb)(5-mebipy)], the cis-[Ru(NO2)2(dppb)(5- mebipy)], the ct-[RuCl(NO)(dppb)(5-mebipy)](PF6)2, and the cc- [RuCl(CH3CN)(dppb)(5-mebipy)]PF6 [dppb = 1,4-bis(diphenylphosphino)butane and 5-mebipy = 5,5´-dimetyl-2,2´-bipyridine] were synthesized and characterized by means of elemental analysis, IR/UV/Vis spectroscopies, cyclic voltammetry, pulse differential voltammetry, NMR 31P{1H}, molar conductivity, and when was the case, by X-ray crystallography. It was showed that for the cis-[RuCl(L)(dppb)(5-mebipy)]PF6 complexes the E1/2 values decrease with the increase of the pKa of the L ligand. For the cis- [RuCl(NO2)(dppb)(5-mebipy)] and cis-[Ru(NO2)2(dppb)(5-mebipy)] complexes, the IR data suggested that the NO2 - species are coordinated to the metal throughout the nitrogen forming nitro complexes. This was confirmed by the determination of the Xray structure of the cis-[Ru(NO2)2(dppb)(5-mebipy)] complex, in which, the nitrite ligands are coordinated to the ruthenium throughout the nitrogen. The electrolysis of the ct-[RuCl(NO)(dppb)(5-mebipy)](PF6)2 complex at 300 mV produces the ct-[RuCl(CH3CN)(dppb)(5-mebipy)]PF6 compound (CH3CN trans the phosphorus), which isomerizes to the cc-[RuCl(CH3CN)(dppb)(5-mebipy)]PF6 complex (CH3CN trans the nitrogen), the final product of the process. It was showed that these isomers are formed by the nitrosyl dissociation of the NO from the ct- [RuCl(NO)(dppb)(5-mebipy)](PF6)2 complex without any potential application. This process was followed by 31P{1H} experiments, in which both isomers were detected, and after a few minutes only the cc isomer was present in the solution. The biological assays showed that the complexes synthesized in this work are active against MDA-MB 231 and K-562 tumor cells and present anti-tuberculosis properties. |
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Cruz Júnior, José Wilmo daBatista, Alzir Azevedohttp://lattes.cnpq.br/6469642481998660http://lattes.cnpq.br/7986883288512102b232c838-3393-49dd-b1ee-7a12ab2e33882016-06-02T20:36:33Z2011-10-172016-06-02T20:36:33Z2010-11-10CRUZ JÚNIOR, José Wilmo da. Phosphine ruthenium complexes containing the ligands nitrite, nitrosyl or pyridines with antitumoral and antituberculosis activities. 2010. 159 f. Dissertação (Mestrado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2010.https://repositorio.ufscar.br/handle/ufscar/6503In this work, a series of cis-[RuCl(L)(dppb)(5-mebipy)]PF6 (L=pyridine, 4- metylpyridine, 4-phenylpyridine, 4-vinylpyridine, 4-terc-butylpyridine and 4- aminopyridine); the cis-[RuCl(NO2)(dppb)(5-mebipy)], the cis-[Ru(NO2)2(dppb)(5- mebipy)], the ct-[RuCl(NO)(dppb)(5-mebipy)](PF6)2, and the cc- [RuCl(CH3CN)(dppb)(5-mebipy)]PF6 [dppb = 1,4-bis(diphenylphosphino)butane and 5-mebipy = 5,5´-dimetyl-2,2´-bipyridine] were synthesized and characterized by means of elemental analysis, IR/UV/Vis spectroscopies, cyclic voltammetry, pulse differential voltammetry, NMR 31P{1H}, molar conductivity, and when was the case, by X-ray crystallography. It was showed that for the cis-[RuCl(L)(dppb)(5-mebipy)]PF6 complexes the E1/2 values decrease with the increase of the pKa of the L ligand. For the cis- [RuCl(NO2)(dppb)(5-mebipy)] and cis-[Ru(NO2)2(dppb)(5-mebipy)] complexes, the IR data suggested that the NO2 - species are coordinated to the metal throughout the nitrogen forming nitro complexes. This was confirmed by the determination of the Xray structure of the cis-[Ru(NO2)2(dppb)(5-mebipy)] complex, in which, the nitrite ligands are coordinated to the ruthenium throughout the nitrogen. The electrolysis of the ct-[RuCl(NO)(dppb)(5-mebipy)](PF6)2 complex at 300 mV produces the ct-[RuCl(CH3CN)(dppb)(5-mebipy)]PF6 compound (CH3CN trans the phosphorus), which isomerizes to the cc-[RuCl(CH3CN)(dppb)(5-mebipy)]PF6 complex (CH3CN trans the nitrogen), the final product of the process. It was showed that these isomers are formed by the nitrosyl dissociation of the NO from the ct- [RuCl(NO)(dppb)(5-mebipy)](PF6)2 complex without any potential application. This process was followed by 31P{1H} experiments, in which both isomers were detected, and after a few minutes only the cc isomer was present in the solution. The biological assays showed that the complexes synthesized in this work are active against MDA-MB 231 and K-562 tumor cells and present anti-tuberculosis properties.Neste trabalho, uma série de complexos cis-[RuCl(L)(dppb)(5-mebipy)]PF6 (L=piridina, 4-metilpiridina, 4-fenilpiridina, 4-vinilpiridina, 4-terc-butilpiridina e 4- aminopiridina); o cis-[RuCl(NO2)(dppb)(5-mebipy)], o cis-[Ru(NO2)2(dppb)(5- mebipy)], o ct-[RuCl(NO)(dppb)(5-mebipy)](PF6)2, e o cc-[RuCl(CH3CN)(dppb)(5- mebipy)]PF6 [dppb = 1,4-bis(difenilfosfina)butano e 5-mebipy = 5,5´-dimetil-2,2´- bipiridina] foram sintetizados e caracterizados por análise elementar, espectroscopia nas regiões do IR e UV/Vis, voltametria cíclica, voltametria de pulso diferencial, RMN 31P{1H}, condutividade molar, e quando foi o caso, por difração de raios X. Observou-se que para os complexos cis-[RuCl(L)(dppb)(5-mebipy)]PF6 o E1/2 diminuía com o aumento do pKa do ligante L. Para o cis-[RuCl(NO2)(dppb)(5- mebipy)] e o cis-[Ru(NO2)2(dppb)(5-mebipy)] complexos, os dados de IV sugerem que as espécies NO2 - se coordenaram ao metal pelo nitrogênio formando nitrocomplexos. Isto foi confirmado pela determinação da estrutura de raios X do complex cis-[Ru(NO2)2(dppb)(5-mebipy)], no qual, de fato os ligantes nitrito estão coordenados pelo nitrogênio. A eletrólise do complexo ct-[RuCl(NO)(dppb)(5-mebipy)](PF6)2 em 300 mV formou o composto ct-[RuCl(CH3CN)(dppb)(5-mebipy)]PF6 (CH3CN trans ao fósforo), o qual isomeriza para o complexo cc-[RuCl(CH3CN)(dppb)(5-mebipy)]PF6 (CH3CN trans ao nitrogênio), o produto final do processo. Foi mostrado que estes isômeros são formados pela dissociação do NO do ct-[RuCl(NO)(dppb)(5-mebipy)](PF6)2 sem aplicação de nenhum potencial. Este processo foi acompanhado por experimentos de 31P{1H} RMN, nos quais ambos os isômeros foram detectados, e após alguns minutos apenas o isômero cc encontrava-se presente em solução. Os ensaios biológicos mostraram que os complexos sintetizados neste trabalho são ativos contra células tumorais MDA-MB 231 e K-562 e apresentam propriedades antituberculose.Universidade Federal de Sao Carlosapplication/pdfporUniversidade Federal de São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarBRQuímica inorgânicaFosfinaComplexos de rutênioCIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICAComplexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculosePhosphine ruthenium complexes containing the ligands nitrite, nitrosyl or pyridines with antitumoral and antituberculosis activitiesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesis-1-1e62fb48f-fa23-4158-8d60-0b17f006946cinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINAL3814.pdfapplication/pdf1496273https://repositorio.ufscar.br/bitstream/ufscar/6503/1/3814.pdf226684bf3b9696544e49be0a310e399bMD51THUMBNAIL3814.pdf.jpg3814.pdf.jpgIM Thumbnailimage/jpeg8603https://repositorio.ufscar.br/bitstream/ufscar/6503/2/3814.pdf.jpg971bb9a9e4e8f3154b79e5096cc5c936MD52ufscar/65032023-09-18 18:31:11.821oai:repositorio.ufscar.br:ufscar/6503Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:11Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Complexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculose |
dc.title.alternative.eng.fl_str_mv |
Phosphine ruthenium complexes containing the ligands nitrite, nitrosyl or pyridines with antitumoral and antituberculosis activities |
title |
Complexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculose |
spellingShingle |
Complexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculose Cruz Júnior, José Wilmo da Química inorgânica Fosfina Complexos de rutênio CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA |
title_short |
Complexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculose |
title_full |
Complexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculose |
title_fullStr |
Complexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculose |
title_full_unstemmed |
Complexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculose |
title_sort |
Complexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculose |
author |
Cruz Júnior, José Wilmo da |
author_facet |
Cruz Júnior, José Wilmo da |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/7986883288512102 |
dc.contributor.author.fl_str_mv |
Cruz Júnior, José Wilmo da |
dc.contributor.advisor1.fl_str_mv |
Batista, Alzir Azevedo |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/6469642481998660 |
dc.contributor.authorID.fl_str_mv |
b232c838-3393-49dd-b1ee-7a12ab2e3388 |
contributor_str_mv |
Batista, Alzir Azevedo |
dc.subject.por.fl_str_mv |
Química inorgânica Fosfina Complexos de rutênio |
topic |
Química inorgânica Fosfina Complexos de rutênio CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA INORGANICA |
description |
In this work, a series of cis-[RuCl(L)(dppb)(5-mebipy)]PF6 (L=pyridine, 4- metylpyridine, 4-phenylpyridine, 4-vinylpyridine, 4-terc-butylpyridine and 4- aminopyridine); the cis-[RuCl(NO2)(dppb)(5-mebipy)], the cis-[Ru(NO2)2(dppb)(5- mebipy)], the ct-[RuCl(NO)(dppb)(5-mebipy)](PF6)2, and the cc- [RuCl(CH3CN)(dppb)(5-mebipy)]PF6 [dppb = 1,4-bis(diphenylphosphino)butane and 5-mebipy = 5,5´-dimetyl-2,2´-bipyridine] were synthesized and characterized by means of elemental analysis, IR/UV/Vis spectroscopies, cyclic voltammetry, pulse differential voltammetry, NMR 31P{1H}, molar conductivity, and when was the case, by X-ray crystallography. It was showed that for the cis-[RuCl(L)(dppb)(5-mebipy)]PF6 complexes the E1/2 values decrease with the increase of the pKa of the L ligand. For the cis- [RuCl(NO2)(dppb)(5-mebipy)] and cis-[Ru(NO2)2(dppb)(5-mebipy)] complexes, the IR data suggested that the NO2 - species are coordinated to the metal throughout the nitrogen forming nitro complexes. This was confirmed by the determination of the Xray structure of the cis-[Ru(NO2)2(dppb)(5-mebipy)] complex, in which, the nitrite ligands are coordinated to the ruthenium throughout the nitrogen. The electrolysis of the ct-[RuCl(NO)(dppb)(5-mebipy)](PF6)2 complex at 300 mV produces the ct-[RuCl(CH3CN)(dppb)(5-mebipy)]PF6 compound (CH3CN trans the phosphorus), which isomerizes to the cc-[RuCl(CH3CN)(dppb)(5-mebipy)]PF6 complex (CH3CN trans the nitrogen), the final product of the process. It was showed that these isomers are formed by the nitrosyl dissociation of the NO from the ct- [RuCl(NO)(dppb)(5-mebipy)](PF6)2 complex without any potential application. This process was followed by 31P{1H} experiments, in which both isomers were detected, and after a few minutes only the cc isomer was present in the solution. The biological assays showed that the complexes synthesized in this work are active against MDA-MB 231 and K-562 tumor cells and present anti-tuberculosis properties. |
publishDate |
2010 |
dc.date.issued.fl_str_mv |
2010-11-10 |
dc.date.available.fl_str_mv |
2011-10-17 2016-06-02T20:36:33Z |
dc.date.accessioned.fl_str_mv |
2016-06-02T20:36:33Z |
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.citation.fl_str_mv |
CRUZ JÚNIOR, José Wilmo da. Phosphine ruthenium complexes containing the ligands nitrite, nitrosyl or pyridines with antitumoral and antituberculosis activities. 2010. 159 f. Dissertação (Mestrado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2010. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/6503 |
identifier_str_mv |
CRUZ JÚNIOR, José Wilmo da. Phosphine ruthenium complexes containing the ligands nitrite, nitrosyl or pyridines with antitumoral and antituberculosis activities. 2010. 159 f. Dissertação (Mestrado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2010. |
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https://repositorio.ufscar.br/handle/ufscar/6503 |
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openAccess |
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Universidade Federal de São Carlos |
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UFSCar |
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BR |
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Universidade Federal de São Carlos |
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