https://repositorio.ufba.br/handle/ri/6443
Campo DC | Valor | Idioma |
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dc.contributor.author | Tfouni, Elia | - |
dc.contributor.author | Macêdo, Antônio Marcos de Souza | - |
dc.contributor.author | Cardoso, Luciana Nunes | - |
dc.contributor.author | Ferreira, Kleber Queiroz | - |
dc.contributor.author | Oliveira, Érica Cristina de | - |
dc.contributor.author | Rocha, Zênis Novais da | - |
dc.creator | Tfouni, Elia | - |
dc.creator | Macêdo, Antônio Marcos de Souza | - |
dc.creator | Cardoso, Luciana Nunes | - |
dc.creator | Ferreira, Kleber Queiroz | - |
dc.creator | Oliveira, Érica Cristina de | - |
dc.creator | Rocha, Zênis Novais da | - |
dc.date.accessioned | 2012-07-17T15:31:54Z | - |
dc.date.issued | 2005 | - |
dc.identifier.issn | 0020-1693 | - |
dc.identifier.uri | http://www.repositorio.ufba.br/ri/handle/ri/6443 | - |
dc.description | Trabalho completo: acesso restrito, p. 2909–2920 | pt_BR |
dc.description.abstract | he 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. | pt_BR |
dc.language.iso | en | pt_BR |
dc.publisher | Elsevier | pt_BR |
dc.source | http://dx.doi.org/10.1016/j.ica.2004.09.008 | pt_BR |
dc.subject | Ruthenium | pt_BR |
dc.subject | dicyanobenzene | pt_BR |
dc.subject | Cyanobenzamide | pt_BR |
dc.subject | Neighboring group participation | pt_BR |
dc.subject | Nitrile hydrolysis | pt_BR |
dc.title | Reactions of pentaammineruthenium complexes with 1,2- and 1,4-dicyanobenzene and cyanobenzamides: evidences of neighboring group participation | pt_BR |
dc.title.alternative | Inorganica Chimica Acta | pt_BR |
dc.type | Artigo de Periódico | pt_BR |
dc.identifier.number | v. 358, n.10 | pt_BR |
dc.embargo.liftdate | 10000-01-01 | - |
Aparece nas coleções: | Artigo Publicado em Periódico (Química) |
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