Kinetics, mechanism, and spectroscopy of the reversible binding of nitric oxide to aquated iron(II) : an undergraduate text book reaction revisited

2002
journal article
article
138
cris.lastimport.wos2024-04-09T22:28:23Z
dc.abstract.enA 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.affiliationWydział Chemii : Zakład Chemii Nieorganicznejpl
dc.contributor.authorWanat, Alicjapl
dc.contributor.authorSchneppensieper, Thorstenpl
dc.contributor.authorStochel, Grażyna - 132108 pl
dc.contributor.authorvan Eldik, Rudi - 239234 pl
dc.contributor.authorBill, Eckhardpl
dc.contributor.authorWieghardt, Karlpl
dc.date.accessioned2015-09-01T07:22:41Z
dc.date.available2015-09-01T07:22:41Z
dc.date.issued2002pl
dc.description.admin[AU] van Eldik, Rudi [SAP14007947]pl
dc.description.number1pl
dc.description.physical4-10pl
dc.description.volume41pl
dc.identifier.doi10.1021/ic010628qpl
dc.identifier.eissn1520-510Xpl
dc.identifier.issn0020-1669pl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/15187
dc.languageengpl
dc.language.containerengpl
dc.rightsDodaję tylko opis bibliograficzny*
dc.rights.licencebez licencji
dc.rights.uri*
dc.subtypeArticlepl
dc.titleKinetics, mechanism, and spectroscopy of the reversible binding of nitric oxide to aquated iron(II) : an undergraduate text book reaction revisitedpl
dc.title.journalInorganic Chemistrypl
dc.typeJournalArticlepl
dspace.entity.typePublication
cris.lastimport.wos
2024-04-09T22:28:23Z
dc.abstract.enpl
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.
dc.affiliationpl
Wydział Chemii : Zakład Chemii Nieorganicznej
dc.contributor.authorpl
Wanat, Alicja
dc.contributor.authorpl
Schneppensieper, Thorsten
dc.contributor.authorpl
Stochel, Grażyna - 132108
dc.contributor.authorpl
van Eldik, Rudi - 239234
dc.contributor.authorpl
Bill, Eckhard
dc.contributor.authorpl
Wieghardt, Karl
dc.date.accessioned
2015-09-01T07:22:41Z
dc.date.available
2015-09-01T07:22:41Z
dc.date.issuedpl
2002
dc.description.adminpl
[AU] van Eldik, Rudi [SAP14007947]
dc.description.numberpl
1
dc.description.physicalpl
4-10
dc.description.volumepl
41
dc.identifier.doipl
10.1021/ic010628q
dc.identifier.eissnpl
1520-510X
dc.identifier.issnpl
0020-1669
dc.identifier.uri
http://ruj.uj.edu.pl/xmlui/handle/item/15187
dc.languagepl
eng
dc.language.containerpl
eng
dc.rights*
Dodaję tylko opis bibliograficzny
dc.rights.licence
bez licencji
dc.rights.uri*
dc.subtypepl
Article
dc.titlepl
Kinetics, mechanism, and spectroscopy of the reversible binding of nitric oxide to aquated iron(II) : an undergraduate text book reaction revisited
dc.title.journalpl
Inorganic Chemistry
dc.typepl
JournalArticle
dspace.entity.type
Publication
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