Structure and reactivity of the prototype iron–oxide cluster Fe2O2+

Jackson, P.; Harvey, Jeremy N.; Schröder, Detlef; Schwarz, Helmut

doi:10.1016/s1387-3806(00)00361-4

Cited by 44 publications

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“…With regard to the reverse process, Fe 2 O 2 ϩ indeed is known to react with two equivalents of H 2 S to yield Fe 2 S 2 ϩ . [21] This observation indicates that hydrolysis of Fe 2 S 2 ϩ is prohibited for thermochemical reasons. Compared with Fe 2 S 2 ϩ , the higher reactivity of Fe 2 O 2 ϩ is also evident from its ability to attack non-activated hydrocarbons such as n-butane.…”

Section: Reactivity Of Fementioning

confidence: 99%

“…Compared with Fe 2 S 2 ϩ , the higher reactivity of Fe 2 O 2 ϩ is also evident from its ability to attack non-activated hydrocarbons such as n-butane. [20,21] Obviously, the metal core cannot fully compensate for the electron deficiency of the O atoms such that the latter exhibit a high affinity for oxidation reactions. For Fe 2 S 2 ϩ , the lower electronegativity of sulfur leads to a better balanced electronic structure in this cluster and a significantly reduced oxidative power.…”

Section: Reactivity Of Fementioning

confidence: 99%

“…Moreover, a comparison with the analogous Fe n O x ϩ ions promised to be most revealing for the dinuclear systems because Fe 2 O 2 ϩ has been studied extensively. [20,21] Ϫ7 mbar], thus again suggesting radiative rather than termolecular relaxation of the association complexes. Compared with H 2 O, the enhanced reactivity of NH 3 reflects its higher basicity that leads to a stronger dative binding which in turn raises the lifetime of the energetic ion-molecule complexes, see above.…”

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Formation and Reactivity of Gaseous Iron‐Sulfur Clusters

2003

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The gas‐phase reactions of Fen+ clusters, n = 1−6, with COS and CS2 have been investigated by means of Fourier‐transform ion‐cyclotron resonance mass spectrometry. Whereas CS2 predominantly substitutes one Fe atom, COS exclusively affords multiple sulfur transfer and thus opens a synthetic route to gaseous FenSx+ clusters. In the final products such as Fe2S2+, Fe3S2+, and Fe4S4+, the sulfur atoms appear to occupy multiple coordination sites much like in the analogous biogeneous iron‐sulfur clusters. Bracketing experiments find IE(Fe2S2) = 7.2±0.3 eV besides providing upper limits for IE(Fe3S2) and IE(Fe4S4). In accordance with the low IE(Fe2S2), Fe2S2+ does not activate H2 or small hydrocarbons and only exhibits rather limited reactivity towards more reactive substrates. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Reactivity Of Fementioning

confidence: 99%

Section: Reactivity Of Fementioning

confidence: 99%

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Formation and Reactivity of Gaseous Iron‐Sulfur Clusters

2003

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“…Die Analyse der kinetischen Daten liefert Geschwindig- 28] dehydrieren Ethen unter diesen milden Bedingungen. Leider können die für diese Reaktionen vorgeschlagenen Mechanismen nicht einfach auf die größeren VPO-Cluster übertragen werden, und erste quantenchemische Rechnungen deuten auf eine recht komplexe Potentialhyperfläche hin, deren Analyse einer eigenen Untersuchung vorbehalten bleiben muss.…”

Section: Professor Giulia De Petris Gewidmetunclassified

Darstellung, Reaktivität gegenüber Kohlenwasserstoffen und elektronische Struktur von heteronuclearen Vanadium‐Phosphor‐Sauerstoff‐Clusterionen

et al. 2011

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Die Mischung macht's! Das Zusammenspiel aus anorganischer Synthese, Massenspektrometrie und quantenchemischen Rechnungen machte die Titel‐Clusterionen [VnP4−nO10].+ (n=2, 3) zugänglich und ermöglichte die Untersuchung ihrer Reaktivität gegenüber CH4, C2H4 und C2H6. Neben der erwarteten C‐H‐Bindungsaktivierung von Methan wurde auch eine unerwartete Produktverteilung mit den beiden C2‐Kohlenwasserstoffen beobachtet.

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“…The Schwarz group has been actively involved in research in the field of gas-phase reactivity, thermochemistry and structure of metal-containing ions that are amenable to mass spectrometry approaches. Recent accounts dealing with ion chemistry of iron chloride and oxide clusters are particularly worth mentioning [6,7].…”

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Reactivity and binding energies of transition metal halide ions with benzene

Gapeev

Dunbar

2002

J. Am. Soc. Mass Spectrom.

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We have generated novel halogen-ligated transition metal ions MX n ϩ (M ϭ Sc, Ti, V, and Fe, X ϭ Cl, Br and I, n ϭ 1 Ϫ 3). We have explored their reactions with benzene, a typical aromatic hydrocarbon. Attachment of one benzene molecule is usually rapid, whereas attachment of a second benzene molecule is generally much slower. The kinetics were analyzed to estimate binding energies, modeling the attachment reaction as a radiative association process. In all cases the Standard Hydrocarbon semiquantitative estimation approach was employed, and in some cases the more accurate variational transition state (VTST) kinetic modeling approach was also applied. Density functional (DFT) quantum calculations were also performed to give computed binding energies for some of the complexes. Taking previously determined binding energies for halogen-ligated alkaline-earth ions as benchmarks, it is concluded that binding of the first benzene molecule to the transition-metal species is strongly enhanced by specific chemical interactions, while binding of the second benzene molecule is more nearly electrostatic. The binding energies are not strongly dependent on the identity of the transition metal ion, and the metal-ion dependences can be rationalized in terms of valence-orbital occupations of the metals. The binding energies are nearly independent of the identity of the halogen ligands. . Cation-pi interactions in biological systems involve metal ions in their stable oxidation state (ϩ1 for alkali metals, ϩ2 for alkaline-earth metals, usually ϩ2 and ϩ3 for the transition metals). This means that gas-phase studies of singly charged systems have direct biological relevance for the alkali ions, but have less clear relevance for most other metal ions. However, using double or triply charged gas-phase metal ions in the absence of solvent leveling introduces large electrostatic interactions that are likely to swamp the chemical interactions one would like to study in the gas phase. A way to resolve this dilemma is to attach ligands to the singly charged metal, thereby raising its oxidation state to its biologically relevant value. Halogen ligands seem to be the best choice because they do not migrate from the metal center nor do they promote ion-molecule reactions.Our previous work in pursuit of this strategy [2] investigated the reactions and binding energies of singly charged, halogenated alkaline-earth metal ions with benzene and mesitylene. The binding energies of the halogen-metal ions to benzene were greatly enhanced relative to the bare metal ions, although still much smaller than the predicted binding energies of bare doubly charged ions. It appeared that the binding in these cases was well described as electrostatic in nature, and that the MX ϩ ions showed behavior intermediate between singly-charged and doubly-charged character. A useful description was that the halogenated metal ions behaved toward the benzene ligand with an effective charge between ϩ1 and ϩ2. For MgCl ϩ a simple classical-electrostatic analysis suggested an...

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Structure and reactivity of the prototype iron–oxide cluster Fe2O2+

Cited by 44 publications

References 44 publications

Formation and Reactivity of Gaseous Iron‐Sulfur Clusters

Formation and Reactivity of Gaseous Iron‐Sulfur Clusters

Darstellung, Reaktivität gegenüber Kohlenwasserstoffen und elektronische Struktur von heteronuclearen Vanadium‐Phosphor‐Sauerstoff‐Clusterionen

Reactivity and binding energies of transition metal halide ions with benzene

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