Complexos fosfínicos de rutênio contendo os ligantes nitro, nitrosilo ou piridinas, com atividades antitumorais e antituberculose

Detalhes bibliográficos
Autor(a) principal: Cruz Júnior, José Wilmo da
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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spelling 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
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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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