Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation

Detalhes bibliográficos
Autor(a) principal: Tfouni, Elia
Data de Publicação: 2005
Outros Autores: Macêdo, Antônio Marcos de Souza, Cardoso, Luciana Nunes, Ferreira, Kleber Queiroz, Oliveira, Érica Cristina de, Rocha, Zênis Novais da
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da UFBA
Texto Completo: http://www.repositorio.ufba.br/ri/handle/ri/6443
Resumo: Trabalho completo: acesso restrito, p. 2909–2920
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spelling Tfouni, EliaMacêdo, Antônio Marcos de SouzaCardoso, Luciana NunesFerreira, Kleber QueirozOliveira, Érica Cristina deRocha, Zênis Novais daTfouni, EliaMacêdo, Antônio Marcos de SouzaCardoso, Luciana NunesFerreira, Kleber QueirozOliveira, Érica Cristina deRocha, Zênis Novais da2012-07-17T15:31:54Z20050020-1693http://www.repositorio.ufba.br/ri/handle/ri/6443v. 358, n.10Trabalho completo: acesso restrito, p. 2909–2920he spectral (UV–Vis and IR) and electrochemical behavior of the nitrile bonded complexes [Ru(NH3)5L]2+ (L = 1,4-dicyanobenzene (1,4-dcb), 1,2-dicyanobenzene (1,2-dcb)), [Ru(NH3)5(NHC(OH)-bz-4-CN)]3+, [Ru(NH3)5(NHC(O)-bz-2-CN)]2+ and [Ru(NH3)5(NH(C)NHC(O)bz)]3+ (NH(C)NHC(O)-bz = 3-imino-1-oxo-isoindoline) are described. Oxidation of [Ru(NH3)5L]2+, at 0 ⩽ pH ⩾ 6, is followed by hydrolysis of the coordinated nitrile to give amide complexes in which the amide is through the nitrogen, with pH-dependent rate constants. The estimated values of the rate constant of hydrolysis (kobs) at 25 °C are 2.9 × 10−3 s−1 for [Ru(NH3)5(1,4-dcb)]3+ and 5.6 × 10−3 s−1 for [Ru(NH3)5(1,2-dcb)]3+ at pH 4.65. Reduction of [Ru(NH3)5(NHC(O)-bz-4-CN)]2+ and [Ru(NH3)5(NHC(O)-bz-2-CN)]2+ is followed by two reactions, one is an aquation forming [Ru(NH3)5(OH2)]2+ and free ligand, and the other an intramolecular linkage isomerization forming [Ru(NH3)5(NC-bz-4-NH2C(O))]2+ and [Ru(NH3)5(NC-bz-2-NH2C(O))]2+. The oxidized1,2-cyanobenzamide complex [Ru(NH3)5(NHC(OH)-bz-2-CN)]3+ undergoes an amide to nitrile intramolecular linkage isomerization, followed by a cyclization reaction resulting in [Ru(NH3)5(NH-(C)(HN-C(O)-2-bz))]3+ ((NH-(C)(HN-C(O)-2-bz)) = 3-imino-1-oxo-isoindoline bonded through the exocyclic nitrogen) (pKa = 4.3). The rates of these reactions, which occur with neighboring group participation, increase with acidity. The reduced form, [Ru(NH3)5(NH-(C)(HN-C(O)-2-bz))]2+, is relatively substitution inert.Submitted by Bruna Lessa (lessbruna@gmail.com) on 2012-07-17T15:31:54Z No. of bitstreams: 1 (127).pdf: 469040 bytes, checksum: b621696566f5e9f6d9dbfaed6ab8422c (MD5)Made available in DSpace on 2012-07-17T15:31:54Z (GMT). No. of bitstreams: 1 (127).pdf: 469040 bytes, checksum: b621696566f5e9f6d9dbfaed6ab8422c (MD5) Previous issue date: 2005-06-15Elsevierhttp://dx.doi.org/10.1016/j.ica.2004.09.008reponame:Repositório Institucional da UFBAinstname:Universidade Federal da Bahia (UFBA)instacron:UFBARutheniumdicyanobenzeneCyanobenzamideNeighboring group participationNitrile hydrolysisReactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participationInorganica Chimica Actainfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article10000-01-01enginfo:eu-repo/semantics/openAccessORIGINAL(127).pdf(127).pdfapplication/pdf469040https://repositorio.ufba.br/bitstream/ri/6443/1/%28127%29.pdfb621696566f5e9f6d9dbfaed6ab8422cMD51LICENSElicense.txtlicense.txttext/plain1762https://repositorio.ufba.br/bitstream/ri/6443/2/license.txt1b89a9a0548218172d7c829f87a0eab9MD52TEXT(127).pdf.txt(127).pdf.txtExtracted texttext/plain51387https://repositorio.ufba.br/bitstream/ri/6443/3/%28127%29.pdf.txtb34f0cdf0ac2b6e8cdaa71062ac40d6cMD53ri/64432022-11-03 14:19:03.012oai:repositorio.ufba.br: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Repositório InstitucionalPUBhttp://192.188.11.11:8080/oai/requestopendoar:19322022-11-03T17:19:03Repositório Institucional da UFBA - Universidade Federal da Bahia (UFBA)false
dc.title.pt_BR.fl_str_mv Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation
dc.title.alternative.pt_BR.fl_str_mv Inorganica Chimica Acta
title Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation
spellingShingle Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation
Tfouni, Elia
Ruthenium
dicyanobenzene
Cyanobenzamide
Neighboring group participation
Nitrile hydrolysis
title_short Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation
title_full Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation
title_fullStr Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation
title_full_unstemmed Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation
title_sort Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation
author Tfouni, Elia
author_facet Tfouni, Elia
Macêdo, Antônio Marcos de Souza
Cardoso, Luciana Nunes
Ferreira, Kleber Queiroz
Oliveira, Érica Cristina de
Rocha, Zênis Novais da
author_role author
author2 Macêdo, Antônio Marcos de Souza
Cardoso, Luciana Nunes
Ferreira, Kleber Queiroz
Oliveira, Érica Cristina de
Rocha, Zênis Novais da
author2_role author
author
author
author
author
dc.contributor.author.fl_str_mv Tfouni, Elia
Macêdo, Antônio Marcos de Souza
Cardoso, Luciana Nunes
Ferreira, Kleber Queiroz
Oliveira, Érica Cristina de
Rocha, Zênis Novais da
Tfouni, Elia
Macêdo, Antônio Marcos de Souza
Cardoso, Luciana Nunes
Ferreira, Kleber Queiroz
Oliveira, Érica Cristina de
Rocha, Zênis Novais da
dc.subject.por.fl_str_mv Ruthenium
dicyanobenzene
Cyanobenzamide
Neighboring group participation
Nitrile hydrolysis
topic Ruthenium
dicyanobenzene
Cyanobenzamide
Neighboring group participation
Nitrile hydrolysis
description Trabalho completo: acesso restrito, p. 2909–2920
publishDate 2005
dc.date.issued.fl_str_mv 2005
dc.date.accessioned.fl_str_mv 2012-07-17T15:31:54Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://www.repositorio.ufba.br/ri/handle/ri/6443
dc.identifier.issn.none.fl_str_mv 0020-1693
dc.identifier.number.pt_BR.fl_str_mv v. 358, n.10
identifier_str_mv 0020-1693
v. 358, n.10
url http://www.repositorio.ufba.br/ri/handle/ri/6443
dc.language.iso.fl_str_mv eng
language eng
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.pt_BR.fl_str_mv http://dx.doi.org/10.1016/j.ica.2004.09.008
dc.source.none.fl_str_mv reponame:Repositório Institucional da UFBA
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