Estudos eletroquÃmicos e de teoria do funcional da densidade(DFT) de nitrosilocomplexos de rutÃnio

Detalhes bibliográficos
Autor(a) principal: SÃrgio Xavier Barbosa AraÃjo
Data de Publicação: 2007
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Biblioteca Digital de Teses e Dissertações da UFC
Texto Completo: http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=1641
Resumo: In this work was performed the study of electrochemical NO release and DFT calculations of nitrosylcomplexes of ruthenium like cis,trans-[Ru(bpy)2LNO]3+, where L= isonicotinamide, imidazole e sulfite, and trans-[Ru(NH3)4LNO]3+, where L= caffeine e theophylline bound by the carbon atom, with the purpose of identify trends and contribute to modulation of new compounds. The electrochemical study of the species has shown that the compounds can release NO after reduction and the rate constant is dependent of the Lligand coordinated to the metallic center. The rates were calculated by double step chronoamperometry and range from 0,183 s-1 for cis-[Ru(bpy)2ImNNO]3+ to3 s-1 for trans-[Ru(NH3)4(theophylline)NO]3+. The DFT study was performed with two functionals, LDA â PWC and GGA â BLYP, to verify the relationship between the theorical calculation conditions and the proximity to the experimental data. The LDA â PWC functional has shown shorter bond lengths and larger charges in NO group and larges NO stretching frequency in FT-IR calculated spectra as well, than the GGA â BLYP functional. The relation between the DFT results and experimental data was good, with linear behavior and r ≈ 0,9. The LDA â PWC gave best fits in the relations.
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spelling info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisEstudos eletroquÃmicos e de teoria do funcional da densidade(DFT) de nitrosilocomplexos de rutÃnioStudies electrochemical and of theory of the funcionary of the density (DFT) of nitrosylcomplexes of ruthenium2007-03-02Luiz Gonzaga de FranÃa Lopes59700920453Luiz Constantino Grombone Vasconcellos04749754870http://lattes.cnpq.br/5834049230321121Gerd Bruno da Rocha83750401420http://lattes.cnpq.br/940494585855509696670347391http://lattes.cnpq.br/3075068541443460SÃrgio Xavier Barbosa AraÃjoUniversidade Federal do CearÃPrograma de PÃs-GraduaÃÃo em QuÃmica InorgÃnicaUFCBRComposites of coordination chronoamperometry theoretical chemistryCompostos de coordenaÃÃo cronoamperometria quÃmica teÃricaQUIMICA INORGANICAIn this work was performed the study of electrochemical NO release and DFT calculations of nitrosylcomplexes of ruthenium like cis,trans-[Ru(bpy)2LNO]3+, where L= isonicotinamide, imidazole e sulfite, and trans-[Ru(NH3)4LNO]3+, where L= caffeine e theophylline bound by the carbon atom, with the purpose of identify trends and contribute to modulation of new compounds. The electrochemical study of the species has shown that the compounds can release NO after reduction and the rate constant is dependent of the Lligand coordinated to the metallic center. The rates were calculated by double step chronoamperometry and range from 0,183 s-1 for cis-[Ru(bpy)2ImNNO]3+ to3 s-1 for trans-[Ru(NH3)4(theophylline)NO]3+. The DFT study was performed with two functionals, LDA â PWC and GGA â BLYP, to verify the relationship between the theorical calculation conditions and the proximity to the experimental data. The LDA â PWC functional has shown shorter bond lengths and larger charges in NO group and larges NO stretching frequency in FT-IR calculated spectra as well, than the GGA â BLYP functional. The relation between the DFT results and experimental data was good, with linear behavior and r ≈ 0,9. The LDA â PWC gave best fits in the relations. Neste trabalho foi realizado o estudo de liberaÃÃo de NO por meio de processos eletroquÃmicos e cÃlculos de DFT de nitrosilocomplexos de rutÃnio do tipo cis,trans-[Ru(bpy)2LNO]3+, onde L= isonicotinamida, imidazol e sulfito, e do tipo trans-[Ru(NH3)4LNO]3+, onde L= imidazol, cafeÃna e teofileno coordenados via carbono, com o objetivo de relacionar propriedades experimentais a resultados de cÃlculos teÃricos para identificar tendÃncias e contribuir para a modulaÃÃo de novos compostos. O estudo eletroquÃmico das espÃcies mostrou que os compostos podem liberar o NO apÃs reduÃÃo do NO no complexo e que a constante de liberaÃÃo à dependente do ligante L coordenado ao centro metÃlico. As constantes foram calculadas pela cronoamperometria de dupla varredura e variaram de 0,183 s-1 para o complexo cis-[Ru(bpy)2ImNNO]3+ a 3 s-1 para o complexo trans-[Ru(NH3)4(teofileno)NO]3+.O estudo por DFT foi realizado com dois funcionais, LDA â PWC e GGAâ BLYP, de modo a verificar a relaÃÃo entre as condiÃÃes de cÃlculo e proximidade dos dados obtidos com os resultados experimentais. O funcional LDA â PWC mostrou menores comprimentos de ligaÃÃo e maiores valores de carga no grupo NO e na banda de estiramento NO no espectro calculado de infravermelho que o funcional GGA- BLYP. Os cÃlculos de DFT para os complexos mostraram boa correlaÃÃo quando seus resultados foram comparados a propriedades experimentais dos complexos, em correlaÃÃes lineares com r ≈ 0,9. O funcional LDA â PWC forneceu as melhores correlaÃÃes.CoordenaÃÃo de AperfeiÃoamento de NÃvel Superiorhttp://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=1641application/pdfinfo:eu-repo/semantics/openAccessporreponame:Biblioteca Digital de Teses e Dissertações da UFCinstname:Universidade Federal do Cearáinstacron:UFC2019-01-21T11:14:40Zmail@mail.com -
dc.title.pt.fl_str_mv Estudos eletroquÃmicos e de teoria do funcional da densidade(DFT) de nitrosilocomplexos de rutÃnio
dc.title.alternative..fl_str_mv Studies electrochemical and of theory of the funcionary of the density (DFT) of nitrosylcomplexes of ruthenium
title Estudos eletroquÃmicos e de teoria do funcional da densidade(DFT) de nitrosilocomplexos de rutÃnio
spellingShingle Estudos eletroquÃmicos e de teoria do funcional da densidade(DFT) de nitrosilocomplexos de rutÃnio
SÃrgio Xavier Barbosa AraÃjo
Compostos de coordenaÃÃo
cronoamperometria
quÃmica teÃrica
QUIMICA INORGANICA
title_short Estudos eletroquÃmicos e de teoria do funcional da densidade(DFT) de nitrosilocomplexos de rutÃnio
title_full Estudos eletroquÃmicos e de teoria do funcional da densidade(DFT) de nitrosilocomplexos de rutÃnio
title_fullStr Estudos eletroquÃmicos e de teoria do funcional da densidade(DFT) de nitrosilocomplexos de rutÃnio
title_full_unstemmed Estudos eletroquÃmicos e de teoria do funcional da densidade(DFT) de nitrosilocomplexos de rutÃnio
title_sort Estudos eletroquÃmicos e de teoria do funcional da densidade(DFT) de nitrosilocomplexos de rutÃnio
author SÃrgio Xavier Barbosa AraÃjo
author_facet SÃrgio Xavier Barbosa AraÃjo
author_role author
dc.contributor.advisor1.fl_str_mv Luiz Gonzaga de FranÃa Lopes
dc.contributor.advisor1ID.fl_str_mv 59700920453
dc.contributor.referee1.fl_str_mv Luiz Constantino Grombone Vasconcellos
dc.contributor.referee1ID.fl_str_mv 04749754870
dc.contributor.referee1Lattes.fl_str_mv http://lattes.cnpq.br/5834049230321121
dc.contributor.referee2.fl_str_mv Gerd Bruno da Rocha
dc.contributor.referee2ID.fl_str_mv 83750401420
dc.contributor.referee2Lattes.fl_str_mv http://lattes.cnpq.br/9404945858555096
dc.contributor.authorID.fl_str_mv 96670347391
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/3075068541443460
dc.contributor.author.fl_str_mv SÃrgio Xavier Barbosa AraÃjo
contributor_str_mv Luiz Gonzaga de FranÃa Lopes
Luiz Constantino Grombone Vasconcellos
Gerd Bruno da Rocha
dc.subject.por.fl_str_mv Compostos de coordenaÃÃo
cronoamperometria
quÃmica teÃrica
topic Compostos de coordenaÃÃo
cronoamperometria
quÃmica teÃrica
QUIMICA INORGANICA
dc.subject.cnpq.fl_str_mv QUIMICA INORGANICA
dc.description.sponsorship.fl_txt_mv CoordenaÃÃo de AperfeiÃoamento de NÃvel Superior
dc.description.abstract..fl_txt_mv In this work was performed the study of electrochemical NO release and DFT calculations of nitrosylcomplexes of ruthenium like cis,trans-[Ru(bpy)2LNO]3+, where L= isonicotinamide, imidazole e sulfite, and trans-[Ru(NH3)4LNO]3+, where L= caffeine e theophylline bound by the carbon atom, with the purpose of identify trends and contribute to modulation of new compounds. The electrochemical study of the species has shown that the compounds can release NO after reduction and the rate constant is dependent of the Lligand coordinated to the metallic center. The rates were calculated by double step chronoamperometry and range from 0,183 s-1 for cis-[Ru(bpy)2ImNNO]3+ to3 s-1 for trans-[Ru(NH3)4(theophylline)NO]3+. The DFT study was performed with two functionals, LDA â PWC and GGA â BLYP, to verify the relationship between the theorical calculation conditions and the proximity to the experimental data. The LDA â PWC functional has shown shorter bond lengths and larger charges in NO group and larges NO stretching frequency in FT-IR calculated spectra as well, than the GGA â BLYP functional. The relation between the DFT results and experimental data was good, with linear behavior and r ≈ 0,9. The LDA â PWC gave best fits in the relations.
dc.description.abstract.por.fl_txt_mv Neste trabalho foi realizado o estudo de liberaÃÃo de NO por meio de processos eletroquÃmicos e cÃlculos de DFT de nitrosilocomplexos de rutÃnio do tipo cis,trans-[Ru(bpy)2LNO]3+, onde L= isonicotinamida, imidazol e sulfito, e do tipo trans-[Ru(NH3)4LNO]3+, onde L= imidazol, cafeÃna e teofileno coordenados via carbono, com o objetivo de relacionar propriedades experimentais a resultados de cÃlculos teÃricos para identificar tendÃncias e contribuir para a modulaÃÃo de novos compostos. O estudo eletroquÃmico das espÃcies mostrou que os compostos podem liberar o NO apÃs reduÃÃo do NO no complexo e que a constante de liberaÃÃo à dependente do ligante L coordenado ao centro metÃlico. As constantes foram calculadas pela cronoamperometria de dupla varredura e variaram de 0,183 s-1 para o complexo cis-[Ru(bpy)2ImNNO]3+ a 3 s-1 para o complexo trans-[Ru(NH3)4(teofileno)NO]3+.O estudo por DFT foi realizado com dois funcionais, LDA â PWC e GGAâ BLYP, de modo a verificar a relaÃÃo entre as condiÃÃes de cÃlculo e proximidade dos dados obtidos com os resultados experimentais. O funcional LDA â PWC mostrou menores comprimentos de ligaÃÃo e maiores valores de carga no grupo NO e na banda de estiramento NO no espectro calculado de infravermelho que o funcional GGA- BLYP. Os cÃlculos de DFT para os complexos mostraram boa correlaÃÃo quando seus resultados foram comparados a propriedades experimentais dos complexos, em correlaÃÃes lineares com r ≈ 0,9. O funcional LDA â PWC forneceu as melhores correlaÃÃes.
description In this work was performed the study of electrochemical NO release and DFT calculations of nitrosylcomplexes of ruthenium like cis,trans-[Ru(bpy)2LNO]3+, where L= isonicotinamide, imidazole e sulfite, and trans-[Ru(NH3)4LNO]3+, where L= caffeine e theophylline bound by the carbon atom, with the purpose of identify trends and contribute to modulation of new compounds. The electrochemical study of the species has shown that the compounds can release NO after reduction and the rate constant is dependent of the Lligand coordinated to the metallic center. The rates were calculated by double step chronoamperometry and range from 0,183 s-1 for cis-[Ru(bpy)2ImNNO]3+ to3 s-1 for trans-[Ru(NH3)4(theophylline)NO]3+. The DFT study was performed with two functionals, LDA â PWC and GGA â BLYP, to verify the relationship between the theorical calculation conditions and the proximity to the experimental data. The LDA â PWC functional has shown shorter bond lengths and larger charges in NO group and larges NO stretching frequency in FT-IR calculated spectra as well, than the GGA â BLYP functional. The relation between the DFT results and experimental data was good, with linear behavior and r ≈ 0,9. The LDA â PWC gave best fits in the relations.
publishDate 2007
dc.date.issued.fl_str_mv 2007-03-02
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/masterThesis
status_str publishedVersion
format masterThesis
dc.identifier.uri.fl_str_mv http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=1641
url http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=1641
dc.language.iso.fl_str_mv por
language por
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Universidade Federal do CearÃ
dc.publisher.program.fl_str_mv Programa de PÃs-GraduaÃÃo em QuÃmica InorgÃnica
dc.publisher.initials.fl_str_mv UFC
dc.publisher.country.fl_str_mv BR
publisher.none.fl_str_mv Universidade Federal do CearÃ
dc.source.none.fl_str_mv reponame:Biblioteca Digital de Teses e Dissertações da UFC
instname:Universidade Federal do Ceará
instacron:UFC
reponame_str Biblioteca Digital de Teses e Dissertações da UFC
collection Biblioteca Digital de Teses e Dissertações da UFC
instname_str Universidade Federal do Ceará
instacron_str UFC
institution UFC
repository.name.fl_str_mv -
repository.mail.fl_str_mv mail@mail.com
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