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dc.typeArtigo de periódicopt_BR
dc.titleCis- And Trans-nitrosyltetraanimineruthenium(ii). Spectral And Electrochemical Properties And Reactivitypt_BR
dc.contributor.authorGomes M.G.pt_BR
dc.contributor.authorDavanzo C.U.pt_BR
dc.contributor.authorSilva S.C.pt_BR
dc.contributor.authorLopes L.G.F.pt_BR
dc.contributor.authorSantos P.S.pt_BR
dc.contributor.authorFranco D.W.pt_BR
unicamp.authorDavanzo, C.U., Instituto de Química, Universidade Estadual de Campinas, Campinas, SP, Brazilpt_BR, M.G., Universidade Federal do Ceará, Departamento de Química Analítica e Físico-Química, Fortaleza, CE, Brazilpt, S.C., Instituto de Química de São Carlos, USP, Caixa Postal 780, 13560-970, São Carlos-SP, Brazilpt, L.G.F., Instituto de Química de São Carlos, USP, Caixa Postal 780, 13560-970, São Carlos-SP, Brazilpt, P.S., Instituto de Química, USP, São Paulo, SP, Brazilpt, D.W., Instituto de Química de São Carlos, USP, Caixa Postal 780, 13560-970, São Carlos-SP, Brazilpt
dc.description.abstractA synthetic route was developed for the preparation of trans-[Ru(NH3)4(NO)X]n++, where X = isonicotinamide (isn), pyrazine (pyz) or sulfite, and cis-[Ru(NH3)4(NO)(NO2)]2+. The complexes have been characterized by elemental analysis, UV/VIS, infrared, 1H NMR and ESR spectroscopies, molar conductance measurements and cyclic voltammetry. All showed v(NO) in the range characteristic of metal-co-ordinated NO+ and do not exhibit any ESR signal, consistent with the formulation of RuII-NO+. The equilibrium constants Keq for the reaction trans-[Ru(NH3)4(NO)X]3+ + 2OH- ⇄ trans-[Ru(NH3)4(NO2)X]+ + H2O are 2.5 × 108 and 6 × 108 dm6 mol-2 for X = isn or pyz. Cyclic voltammograms of the complexes in aqueous solution exhibited reversible one-electron waveforms in the potential range -0.13 to -0.38 V vs. SCE, which were assigned to the [Ru(NH3)4(NO)X]n+ → [Ru(NH3)4(NO)X](n-1)+ process. Nitric oxide and trans-[Ru(NH3)4(H2O)X]2+ are the final products of the reaction between EuII and trans-[Ru(NH3)4(NO)X]3+, L = isn or pyz. Ab initio molecular orbital calculations performed for trans-[Ru(NH3)4(NO)(pyz)]3+ and trans-[Ru(NH3)4(NO)(pyz)]2+, and the products of the trans-[Ru(NH3)4(NO)(pyz)]3+ one-electron electrochemical or chemical reduction, strongly suggest the added electron is localized mainly on the nitrosyl ligand. A correlation was observed between v(NO) and E1/2 for the reversible reduction wave. These results indicate that the nitric oxide reduction is facilitated by strong π-acceptor ligands trans to the NO. Nitric oxide and trans-[Ru(NH3)4(H2O)X]3+ were formed when solutions containing trans-[Ru(NH3)4(NO)X]3+ were irradiated in the range 310-370 nm.en
dc.relation.ispartofJournal of the Chemical Society - Dalton Transactionspt_BR
dc.identifier.citationJournal Of The Chemical Society - Dalton Transactions. , v. , n. 4, p. 601 - 607, 1998.pt_BR
dc.description.provenanceMade available in DSpace on 2015-06-30T15:05:25Z (GMT). No. of bitstreams: 0 Previous issue date: 1998en
dc.description.provenanceMade available in DSpace on 2015-11-26T15:13:29Z (GMT). No. of bitstreams: 0 Previous issue date: 1998en
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