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Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF5]+ and [Xe2F11]+ Salts of the [Cr(VI)OF5]–, [Cr(IV)F6]2–, [Cr(V)OF5]2–, and [Cr(V)2O2F8]2– Anions

preprint
submitted on 18.10.2018 and posted on 19.10.2018 by Daniel G. Stuart, Mark R. Bortolus, James Goettel, Hélène P. A. Mercier, Gary Schrobilgen

Molten mixtures of XeF6 and CrVIOF4 in 1:1 and 1:2 molar ratios undergo reduction to Cr(V) and Cr(IV) by means of F2 elimination to form [XeF5][Xe2F11][CrVOF5]∙2CrVIOF4 and [XeF5]2[CrIVF6]∙2CrVIOF4, respectively, as shown by low-temperature (LT) single-crystal X-ray diffraction (SCXRD). A LT Raman spectroscopic study of an equimolar mixture of solid XeF6 and CrOF4 and its melt showed that [CrVIOF5] is formed as an intermediate. Reaction of [XeF5]2[CrIVF6]∙2CrVIOF4 with XeF6 in a melt gave [Xe2F11]2[CrIVF6] and [XeF5]2[CrV2O2F8]. Their LT crystal structures revealed that [XeF5]+ and [Xe2F11]+ are coordinated to their respective [CrF6]2− and [Cr2O2F8]2− anions by means of Xe---F–Cr bridges to form infinite chain structures. The reactions of a 1:1 molar ratio of XeF6 and CrOF4 in anhydrous hydrogen fluoride (aHF) and in mixed CFCl3/aHF solvents yielded [XeF5]2[CrV2O2F8]∙2HF and a mixture of [XeF5]2[CrV2O2F8]∙2HF and [XeF5]2[CrV2O2F8]∙2XeOF4, respectively. The SCXRD structures of the latter and aforementioned salts provide the first X-ray structures of [CrOF5]2– and [Cr2O2F8]2–. The [XeF5]2[CrV2O2F8]∙2XeOF4 and [XeF5][Xe2F11][CrVOF5]∙2CrVIOF4 salts were also characterized by LT Raman spectroscopy. Quantum-chemical calculations were carried out to obtain the energy-minimized, gas-phase geometries and vibrational frequencies for [CrVIOF5], [XeF5]2[CrV2O2F8]∙2XeOF4, [CrV2O2F8]2–, [XeF5][Xe2F11][CrVOF5]∙2CrVIOF4, [CrVOF5]2–, and to aid in the assignments of their vibrational frequencies.


Funding

NSERC, Discovery Grant (2006-04561)

History

Email Address of Submitting Author

schrobil@mcmaster.ca

Institution

McMaster University

Country

Canada

ORCID For Submitting Author

0000-0001-5109-6979

Declaration of Conflict of Interest

The authors declare no conflict of interest.

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