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Kinetics, mechanism, and spectroscopy of the reversible binding of nitric oxide to aquated iron(II) : an undergraduate text book reaction revisited
A detailed kinetic and mechanistic analysis of the classical "brown-ring" reaction of
| cris.lastimport.wos | 2024-04-09T22:28:23Z | |
| dc.abstract.en | A detailed kinetic and mechanistic analysis of the classical "brown-ring" reaction of $[Fe(H_{2}O)_{6}]^{2+}$ with NO was performed using stopped-flow and laser flash photolysis techniques at ambient and high pressure. The kinetic parameters for the "on" and "off" reactions at 25 $^{o}\textrm{C}$ were found to be $k_{on}$ = 1.42 × $10^{6}$ $M^{-1}$ $s^{-1}$, $\Delta$H⧧$_{on}$ = 37.1 $\pm$ 0.5 kJ $mol^{-1}$, $\Delta$S⧧$_{on}$ = −3 $\pm$ 2 J $K^{-1}$ $mol^{-1}$, $\Delta$V⧧$_{on}$ = +6.1 ± 0.4 $cm^{3}$ $mol^{-1}$, and $k_{off}$ = 3240 $\pm$ 750 $s^{-1}$, $\Delta$H⧧$_{off}$ = 48.4 $\pm$ 1.4 kJ $mol^{-1}$, $\Delta$S⧧$_{off}$ = −15 $\pm$ 5 J $K^{-1}$ $mol^{-1}$, $\Delta$V⧧$_{off}$ = +1.3 $\pm $ 0.2 $cm^{3}$ $mol^{-1}$. These parameters suggest that both reactions follow an interchange dissociative ($I_{d}$) ligand substitution mechanism, which correlates well with the suggested mechanism for the water exchange reaction on $[Fe(H_{2}O)_{6}]^{2+}$. In addition, Mössbauer spectroscopy and EPR measurements were performed on the reaction product $[Fe(H_{2}O)_{5}(NO)]^{2+}$. The Mössbauer and EPR parameters closely resemble those of the ${FeNO}^{7}$ units in any of the other well-characterized nitrosyl complexes. It is concluded that its electronic structure is best described by the presence of high-spin $Fe^{III}$ antiferromagnetically coupled to $NO^{1}$ (S = 1) yielding the observed spin quartet ground state ($S=^{3}/_{2}$), i.e., $[Fe^{III}(H_{2}O)_{5}(NO^{-})]^{2+}$, and not $[Fe^{I}(H_{2}O)_{5}(NO^{-})]^{2+}$ as usually quoted in undergraduate text books. | pl |
| dc.affiliation | Wydział Chemii : Zakład Chemii Nieorganicznej | pl |
| dc.contributor.author | Wanat, Alicja | pl |
| dc.contributor.author | Schneppensieper, Thorsten | pl |
| dc.contributor.author | Stochel, Grażyna - 132108 | pl |
| dc.contributor.author | van Eldik, Rudi - 239234 | pl |
| dc.contributor.author | Bill, Eckhard | pl |
| dc.contributor.author | Wieghardt, Karl | pl |
| dc.date.accessioned | 2015-09-01T07:22:41Z | |
| dc.date.available | 2015-09-01T07:22:41Z | |
| dc.date.issued | 2002 | pl |
| dc.description.admin | [AU] van Eldik, Rudi [SAP14007947] | pl |
| dc.description.number | 1 | pl |
| dc.description.physical | 4-10 | pl |
| dc.description.volume | 41 | pl |
| dc.identifier.doi | 10.1021/ic010628q | pl |
| dc.identifier.eissn | 1520-510X | pl |
| dc.identifier.issn | 0020-1669 | pl |
| dc.identifier.uri | http://ruj.uj.edu.pl/xmlui/handle/item/15187 | |
| dc.language | eng | pl |
| dc.language.container | eng | pl |
| dc.rights | Dodaję tylko opis bibliograficzny | * |
| dc.rights.licence | bez licencji | |
| dc.rights.uri | * | |
| dc.subtype | Article | pl |
| dc.title | Kinetics, mechanism, and spectroscopy of the reversible binding of nitric oxide to aquated iron(II) : an undergraduate text book reaction revisited | pl |
| dc.title.journal | Inorganic Chemistry | pl |
| dc.type | JournalArticle | pl |
| dspace.entity.type | Publication |