The dixenon(1+) cation: Formation in the condensed phases and characterization by ESR, UV-visible, and Raman spectroscopy

Journal Article · Wed Nov 25 04:00:00 EST 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00050a023· OSTI ID:7186864

Brown, D R; Clegg, M J; Downs, A J; Fowler, R C; Minihan, A R ^[1]; Norris, J R; Stein, L ^[2]

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1. Univ. of Oxford (United Kingdom)
2. Argonne National Lab., IL (United States)

The redox chemistry of the couple formed by XeF[sup +] and elemental xenon gives rise to a green intermediate. This is formed, for example, from XeF[sup +]Sb[sub 2]F[sub 11][sup [minus]] in antimony pentafluoride solution, irreversibly under the action of various reducing agents (e.g. H[sub 2]O, Pb, Hg, SO[sub 2], PF[sub 3], or SbF[sub 3]) or reversibly under the action of xenon gas, and while an overpressure of xenon is maintained, it is long-lived at ambient temperatures. The product has been characterized by a combination of ESR, UV-visible, and Raman spectroscopies, enrichment in [sup 136]Xe or [sup 129]Xe playing a crucial role in establishing that the carrier of the green coloration is the dixenon(1+) cation, Xe[sub 2][sup +]. Quantitative studies of the UV-visible and Raman spectra of antimony pentafluoride solutions imply that the reversible formation of Xe[sub 2][sup +] takes place in accordance with the equilibrium 3Xe + XeF[sup +]Sb[sub 2]F[sub 11][sup [minus]] + 2SbF[sub 5] [r reversible] 2Xe[sub 2][sup +]Sb[sub 2]F[sub 11][sup [minus]], although a secondary equilibrium finds the Xe[sub 2][sup +] bound in a complex with an excess of the oxidant: Xe[sub 2][sup +]Sb[sub 2]F[sub 11][sup [minus]] + XeF[sup +]Sb[sub 2]F[sub 11][sup [minus]] [r reversible] Xe[sub 2][sup +]Sb[sub 2]F[sub 11][sup [minus]][center dot]XeF[sup +]Sb[sub 2]F[sub 11][sup [minus]]. The spectroscopic properties of Xe[sub 2][sup +] are discussed in relation to those of the isoelectronic species I[sub 2][sup [minus]] and to the results of previous theoretical calculations. Of the media investigated to date antimony pentafluoride seems to be unique in its ability to support the Xe[sub 2][sup +] cation in appreciable concentrations at normal temperatures.

• OSTI ID: 7186864
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:24; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
CATIONS
CHARGED PARTICLES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
DATA
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
INFORMATION
IONS
LASER SPECTROSCOPY
MAGNETIC RESONANCE
NUMERICAL DATA
OXIDATION
RAMAN SPECTROSCOPY
RARE GAS COMPOUNDS
REDUCTION
RESONANCE
SPECTRA
SPECTROSCOPY
SYNTHESIS
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA
XENON COMPOUNDS
XENON FLUORIDES