An electrospray ionization mass spectrometry study of the nitroprusside-cation-thiolate system

2002
journal article
article
15
cris.lastimport.wos2024-04-09T21:33:30Z
dc.abstract.enThe complex anion $[Fe(CN)_{5}(NO)]^{2-}$ (nitroprusside) has been defined intact using electrospray ionization mass spectrometry (ESIMS), with minor daughter ions predictable fragments of the parent $[Fe(CN)_{5}(NO)]^{2-}$. Direct evidence for ion pairing of $[Fe(CN)_{5}(NO)]^{2-}$ with monovalent alkali metal and some alkylammonium cations was found independently using ESIMS and $^{13}\textrm{C}$ NMR techniques. The results are relevant to the significant influence of the concentration and nature of cations on the solution equilibrium between nitroprusside with thiolates and their nitrosothiol adducts that presumably arises through charge reduction in tight ion pairs facilitating adduct formation. Ion-paired species ${M^{+}[Fe(CN)_{5}NO]^{2-}}^{-}$, ${M_{3}[Fe(CN)_{5}NO]}^{+}$ and more complex clusters of the type ${M_{x}[Fe(CN)_{5}NO]\gamma }^{2-/2+}$ (up to x=8 and y=5) were observed by ESIMS. The trend in the ion pair formation seen by ESIMS follows the series Li$^{+}$ > Na$^{+}$ > K$^{+}$ > Rb$^{+}$ > Cs$^{+}$ and $Me_{4}N^{+}$ > $Et_{4}N^{+}$ > $Pr_{4}N^{+}$ > $Bu_{4}N^{+}$ and is consistent with purely electrostatic expectations for unsolvated ions. Whereas the poorly solvated alkylammonium series bulk solution behaviour resembles that found by the ESI technique, the activity of alkali metal cations proceeds conversely, i.e. Li$^{+}$ < Na$^{+}$ < K$^{+}$ < Rb$^{+}$ < Cs$^{+}$, verified by a $^{13}\textrm{C}$ NMR study, because the hydrated cation radii play a crucial role in the bulk solution in those cases. Differences in changes of the chemical shift upon addition of various cations points to the axial CN$^{-}$ position as especially important for binding to these cations. Further, short-lived adducts with thiolates of the type ${M^{+}_{3}[Fe(CN)_{5}NO(C_{4}H_{4}O_{4}S)]^{4-}}^{-}$ have been defined by their observation in ESIMS directly and through their decomposition products, providing further support for reversible nitrosothiol complex formation. Mercapto- succinate ion pairing with cations, which would make formation of the proposed nitrosothiol complex easier, is also observed by ESIMS. The dithiolato complex ${K^{+}[Fe(CN)_{5}NO(C_{4}H_{6}O_{4}S)_{2}]^{2-}}^{-}$, as well as the disulfide anion radical were detected; both species are suggested intermediates in the spontaneous and autocatalyzed redox decomposition of the $[Fe(CN)_{5}N(O)SR]^{(N+2)-}$ complexes. The ESIMS study has thus provided information relevant to both thermodynamic and kinetic processes in a reaction where species of limited stability are involved.pl
dc.affiliationWydział Chemii : Zakład Chemii Nieorganicznejpl
dc.contributor.authorLawrance, Geoffrey A.pl
dc.contributor.authorMaeder, Marcelpl
dc.contributor.authorNeuhold, Yorck-Michaelpl
dc.contributor.authorSzaciłowski, Konrad - 132185 pl
dc.contributor.authorBarbieri, Andreapl
dc.contributor.authorStasicka, Zofiapl
dc.date.accessioned2015-09-23T07:23:29Z
dc.date.available2015-09-23T07:23:29Z
dc.date.issued2002pl
dc.description.number19pl
dc.description.physical3649-3655pl
dc.identifier.doi10.1039/B205536Hpl
dc.identifier.eissn1364-5447pl
dc.identifier.issn1472-7773pl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/15763
dc.languageengpl
dc.language.containerengpl
dc.rightsDodaję tylko opis bibliograficzny*
dc.rights.licencebez licencji
dc.rights.uri*
dc.subtypeArticlepl
dc.titleAn electrospray ionization mass spectrometry study of the nitroprusside-cation-thiolate systempl
dc.title.journalJournal of the Chemical Society. Dalton Transactionspl
dc.typeJournalArticlepl
dspace.entity.typePublication
cris.lastimport.wos
2024-04-09T21:33:30Z
dc.abstract.enpl
The complex anion $[Fe(CN)_{5}(NO)]^{2-}$ (nitroprusside) has been defined intact using electrospray ionization mass spectrometry (ESIMS), with minor daughter ions predictable fragments of the parent $[Fe(CN)_{5}(NO)]^{2-}$. Direct evidence for ion pairing of $[Fe(CN)_{5}(NO)]^{2-}$ with monovalent alkali metal and some alkylammonium cations was found independently using ESIMS and $^{13}\textrm{C}$ NMR techniques. The results are relevant to the significant influence of the concentration and nature of cations on the solution equilibrium between nitroprusside with thiolates and their nitrosothiol adducts that presumably arises through charge reduction in tight ion pairs facilitating adduct formation. Ion-paired species ${M^{+}[Fe(CN)_{5}NO]^{2-}}^{-}$, ${M_{3}[Fe(CN)_{5}NO]}^{+}$ and more complex clusters of the type ${M_{x}[Fe(CN)_{5}NO]\gamma }^{2-/2+}$ (up to x=8 and y=5) were observed by ESIMS. The trend in the ion pair formation seen by ESIMS follows the series Li$^{+}$ > Na$^{+}$ > K$^{+}$ > Rb$^{+}$ > Cs$^{+}$ and $Me_{4}N^{+}$ > $Et_{4}N^{+}$ > $Pr_{4}N^{+}$ > $Bu_{4}N^{+}$ and is consistent with purely electrostatic expectations for unsolvated ions. Whereas the poorly solvated alkylammonium series bulk solution behaviour resembles that found by the ESI technique, the activity of alkali metal cations proceeds conversely, i.e. Li$^{+}$ < Na$^{+}$ < K$^{+}$ < Rb$^{+}$ < Cs$^{+}$, verified by a $^{13}\textrm{C}$ NMR study, because the hydrated cation radii play a crucial role in the bulk solution in those cases. Differences in changes of the chemical shift upon addition of various cations points to the axial CN$^{-}$ position as especially important for binding to these cations. Further, short-lived adducts with thiolates of the type ${M^{+}_{3}[Fe(CN)_{5}NO(C_{4}H_{4}O_{4}S)]^{4-}}^{-}$ have been defined by their observation in ESIMS directly and through their decomposition products, providing further support for reversible nitrosothiol complex formation. Mercapto- succinate ion pairing with cations, which would make formation of the proposed nitrosothiol complex easier, is also observed by ESIMS. The dithiolato complex ${K^{+}[Fe(CN)_{5}NO(C_{4}H_{6}O_{4}S)_{2}]^{2-}}^{-}$, as well as the disulfide anion radical were detected; both species are suggested intermediates in the spontaneous and autocatalyzed redox decomposition of the $[Fe(CN)_{5}N(O)SR]^{(N+2)-}$ complexes. The ESIMS study has thus provided information relevant to both thermodynamic and kinetic processes in a reaction where species of limited stability are involved.
dc.affiliationpl
Wydział Chemii : Zakład Chemii Nieorganicznej
dc.contributor.authorpl
Lawrance, Geoffrey A.
dc.contributor.authorpl
Maeder, Marcel
dc.contributor.authorpl
Neuhold, Yorck-Michael
dc.contributor.authorpl
Szaciłowski, Konrad - 132185
dc.contributor.authorpl
Barbieri, Andrea
dc.contributor.authorpl
Stasicka, Zofia
dc.date.accessioned
2015-09-23T07:23:29Z
dc.date.available
2015-09-23T07:23:29Z
dc.date.issuedpl
2002
dc.description.numberpl
19
dc.description.physicalpl
3649-3655
dc.identifier.doipl
10.1039/B205536H
dc.identifier.eissnpl
1364-5447
dc.identifier.issnpl
1472-7773
dc.identifier.uri
http://ruj.uj.edu.pl/xmlui/handle/item/15763
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
An electrospray ionization mass spectrometry study of the nitroprusside-cation-thiolate system
dc.title.journalpl
Journal of the Chemical Society. Dalton Transactions
dc.typepl
JournalArticle
dspace.entity.type
Publication

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