Thermodynamics and kinetics of as an efficient scavenger for nitric oxide in aqueous solution

2002
journal article
article
cris.lastimport.scopus2024-04-07T16:22:42Z
dc.abstract.enThe edta complex of $Ru^{III}$ reacts very rapidly with NO in aqueous solution at pH=5 to form a stable nitrosyl complex. The results from FT-IR (ATR) and $^{15}\textrm{N}-NMR$ studies clearly support the $NO^{+}$ character of coordinated NO, such that the nitrosyl product can be formulated as $[Ru^{III}(edta)NO]^{+}$. A combination of UV-Vis spectroscopy and electrochemical detection of NO was used to determine the overall equilibrium constant $K_{NO}$ as (9.1 $\pm$ 1.2) × $10^{7}$ $M^{-1}$ at 25 $^{o}\textrm{C}$ and pH = 5.0. Stopped-flow kinetic studies on the reaction of acetate-buffered solutions of $[Ru^{III}(edta)H_{2}O]^{-}$ with NO gave $k_{on}$ values two orders of magnitude lower than that reported in the literature as a result of buffer effects. The values of $k_{on}$ determined at low and high pH, viz. 3.8 × $10^{4}$ and 1.2 × $10^{5}$ $M^{-1}$ $s^{-1}$, respectively, are significantly smaller than that found at pH = 5.0, and in agreement with that observed for the substitution reactions of $Ru^{III}(edta)$ with other entering nucleophiles. Attempts to determine $k_{on}$ for the binding of NO to $[Ru^{III}(edta)H_{2}O]^{-}$ using laser flash photolysis failed due to the occurrence of side reactions. Under specific conditions (NO in excess and ${NO_{2}}^{-}$ as impurity), the formation of the disubstituted $[Ru^{II}(edta)(NO^{+})({NO_{2}}^{-})]^{2-}$ species was detected using $^{15}\textrm{N}-NMR$ spectroscopy. Laser flash photolysis of this complex leads to multiple chemical reaction steps as a result of the formation of two primary photoproducts, which decay with di fferent rate constants to the starting complex. Possible mechanisms for these photoinduced reactions are proposed and compared to related systems reported in the literature.pl
dc.affiliationWydział Chemii : Zakład Chemii Nieorganicznejpl
dc.contributor.authorWanat, Alicjapl
dc.contributor.authorSchneppensieper, Thorstenpl
dc.contributor.authorKarocki, Andrzejpl
dc.contributor.authorStochel, Grażyna - 132108 pl
dc.contributor.authorvan Eldik, Rudi - 239234 pl
dc.date.accessioned2015-09-22T10:41:25Z
dc.date.available2015-09-22T10:41:25Z
dc.date.issued2002pl
dc.description.admin[AU] van Eldik, Rudi [SAP14007947]pl
dc.description.number6pl
dc.description.physical941-950pl
dc.identifier.doi10.1039/B108236Cpl
dc.identifier.eissn1364-5447pl
dc.identifier.issn1472-7773pl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/15753
dc.languageengpl
dc.language.containerengpl
dc.rightsDodaję tylko opis bibliograficzny*
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dc.subtypeArticlepl
dc.titleThermodynamics and kinetics of $Ru^{III}(edta)$ as an efficient scavenger for nitric oxide in aqueous solutionpl
dc.title.journalJournal of the Chemical Society. Dalton Transactionspl
dc.typeJournalArticlepl
dspace.entity.typePublication

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