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The classic 'brown-ring' reaction in a new medium : kinetics, mechanism, and spectroscopy of the reversible binding of nitric oxide to iron(II) in an ionic liquid

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The classic 'brown-ring' reaction in a new medium : kinetics, mechanism, and spectroscopy of the reversible binding of nitric oxide to iron(II) in an ionic liquid

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dc.contributor.author Begel, Svetlana pl
dc.contributor.author Stopa, Grzegorz [SAP11009008] pl
dc.contributor.author Stochel, Grażyna [SAP11011061] pl
dc.contributor.author van Eldik, Rudi [SAP14007947] pl
dc.contributor.author Heinemann, Frank W. pl
dc.date.accessioned 2015-09-14T09:47:28Z
dc.date.available 2015-09-14T09:47:28Z
dc.date.issued 2011 pl
dc.identifier.issn 0020-1669 pl
dc.identifier.uri http://ruj.uj.edu.pl/xmlui/handle/item/15620
dc.language eng pl
dc.title The classic 'brown-ring' reaction in a new medium : kinetics, mechanism, and spectroscopy of the reversible binding of nitric oxide to iron(II) in an ionic liquid pl
dc.type JournalArticle pl
dc.description.physical 3946-3958 pl
dc.abstract.en To elucidate the applicability and properties of ionic liquids (ILs) to serve as chemical reaction media for the activation of small molecules by transition-metal complexes, detailed kinetic and mechanistic studies were performed on the reversible binding of NO to FeCl 2 dissolved in the IL 1-ethyl-3-methylimidazolium dicyanamide ([emim][dca]) as a solvent. We report, for the fi rst time, the application of laser fl ash photolysis at ambient and high pressure to study the kinetics of this reaction in an IL. The kinetic data and activation parameters for the “ on ” and “ off ” reactions suggest that both processes follow a limiting dissociative (D) ligand substitution mechanism, in contrast to that reported for the same reaction in aqueous solution, where this well-known “ brown-ring ” reaction follows an interchange dissociative (I d ) ligand substitution mechanism. The observed di ff erence apparently arises from the participation of the IL anion as a N-donor ligand, as evidenced by the formation of polymeric [Fe(dca) 3 Cl] x [emim] 2 x chains in the solid state and veri fi ed by X-ray crystallography. In addition, infrared (IR), M € ossbauer, and EPR spectra were recorded for the monomeric reaction product [Fe(dca) 5 NO] 3 formed in the IL, and the parameters closely resemble those ofthe { FeNO } 7 unit inother well-characterized nitrosylcomplexes. Itisconcluded thatits electronic structureisbest described by the presence of a high-spin Fe(III) ( S = 5/2) center antiferromagnetically coupled to NO ( S = 1), yielding the observed spin quartet ground state ( S t = 3/2). pl
dc.description.volume 50 pl
dc.description.number 9 pl
dc.description.points 40 pl
dc.identifier.doi 10.1021/ic1023357 pl
dc.identifier.eissn 1520-510X pl
dc.title.journal Inorganic Chemistry pl
dc.language.container eng pl
dc.affiliation Wydział Chemii : Zakład Chemii Nieorganicznej pl
dc.subtype Article pl
.pointsMNiSW [2011 A]: 40


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