Chromium(VI) Oxyfluoride Dianions, [Cr <subscript>2</subscript> O <subscript>4</subscript> F <subscript>6</subscript> ] <superscript>2-</superscript> and [CrO <subscript>2</subscript> F <subscript>4</subscript> ] <superscript>2-</superscript> ; Syntheses and Structures of [XeF <subscript>5</subscript> ] <subscript>2</subscript> [Cr <subscript>2</subscript> O <subscript>4</subscript> F <subscript>6</subscript> ], [XeF <subscript>5</subscript> ] <subscript>2</subscript> [Cr <subscript>2</subscript> O <subscript>4</subscript> F <subscript>6</subscript> ] ⋅ nX (X=HF, n=4; X=XeOF <subscript>4</subscript> , n=2), and [XeF <subscript>5</subscript> ][Xe <subscript>2</subscript> F <subscript>11</subscript> ][CrO <subscript>2</subscript> F <subscript>4</subscript> ].

Bortolus, MR ; Mercier, HPA ; et al.

In: Chemistry (Weinheim an der Bergstrasse, Germany), Jg. 30 (2024-02-16), Heft 10, S. e202303059

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The fluorobasic character of the strong oxidative fluorinator, XeF 6 , and the oxidative resistance of the [XeF 5 ] + and [Xe 2 F 11 ] + cations have been exploited for the syntheses of several novel Cr(VI) dianion salts. The reactions of XeF 6 and CrO 2 F 2 in anhydrous HF and by direct fusion of the reactants in melts have yielded the first dinuclear Cr(VI) oxyfluoro-dianion salts, [XeF 5 ] 2 [Cr 2 O 4 F 6 ], [XeF 5 ] 2 [Cr 2 O 4 F 6 ] ⋅ 4HF, [XeF 5 ] 2 [Cr 2 O 4 F 6 ] ⋅ 2XeOF 4 , and mononuclear Cr(VI) oxyfluoro-dianion salt, [XeF 5 ][Xe 2 F 11 ][CrO 2 F 4 ]. The salts were structurally characterized by low-temperature (LT) single-crystal X-ray diffraction (SCXRD) and LT Raman spectroscopy. The [CrO 2 F 4 ] 2- and [Cr 2 O 4 F 6 ] 2- dianions have distorted octahedral cis-dioxo Cr(VI) coordination spheres in which two F-atoms are trans to one another and two F-atoms are trans to O-atoms, where the [Cr 2 O 4 F 6 ] 2- dianion is the fluorine-bridged dimer of the [CrO 2 F 3 ] - anion. Quantum-chemical calculations were used to obtain the energy-minimized, gas-phase geometries, and the calculated vibrational spectra of the gas-phase dianions and their ion-pairs, which were used to aid in the vibrational frequency assignments of the crystalline salts. NBO and MEPS analyses and SCXRD show these salts are comprised of intimate ion-pairs in which their cations and anions interact through primarily electrostatic Xe- - -F σ-hole bonds.

Titel:	Chromium(VI) Oxyfluoride Dianions, [Cr <subscript>2</subscript> O <subscript>4</subscript> F <subscript>6</subscript> ] <superscript>2-</superscript> and [CrO <subscript>2</subscript> F <subscript>4</subscript> ] <superscript>2-</superscript> ; Syntheses and Structures of [XeF <subscript>5</subscript> ] <subscript>2</subscript> [Cr <subscript>2</subscript> O <subscript>4</subscript> F <subscript>6</subscript> ], [XeF <subscript>5</subscript> ] <subscript>2</subscript> [Cr <subscript>2</subscript> O <subscript>4</subscript> F <subscript>6</subscript> ] ⋅ nX (X=HF, n=4; X=XeOF <subscript>4</subscript> , n=2), and [XeF <subscript>5</subscript> ][Xe <subscript>2</subscript> F <subscript>11</subscript> ][CrO <subscript>2</subscript> F <subscript>4</subscript> ].
Autor/in / Beteiligte Person:	Bortolus, MR ; Mercier, HPA ; Schrobilgen, GJ
Link:	Full Text Finder (Volltext)
Zeitschrift:	Chemistry (Weinheim an der Bergstrasse, Germany), Jg. 30 (2024-02-16), Heft 10, S. e202303059
Veröffentlichung:	Weinheim, Germany : Wiley-VCH, 2024
Medientyp:	academicJournal
ISSN:	1521-3765 (electronic)
DOI:	10.1002/chem.202303059
Sonstiges:	Nachgewiesen in: MEDLINE Sprachen: English Publication Type: Journal Article Language: English [Chemistry] 2024 Feb 16; Vol. 30 (10), pp. e202303059. <i>Date of Electronic Publication: </i>2024 Jan 02. References: S. Ghammamy, S. Dastpeyman, S. A. S. Sadjadi, Trans. Met. Chem. 2006, 31, 482-486. ; W. Granier, S. Vilminot, J. D. Vidal, L. Cot, J. Fluorine Chem. 1981, 19, 123-134. ; J. P. Chaminade, M. Cervera-Marzal, M. Pouchard, J. Cryst. Growth 1984, 66, 477-479. ; J. P. Chaminade, J. M. Moutou, G. Villeneuve, M. Couzi, M. Pouchard, P. Hagenmuller, J. Solid State Chem. 1986, 65, 27-39. ; K. Nitta, T. Nohira, R. Hagiwara, M. Majima, S. Inazawa, Electrochim. Acta 2010, 55, 1278-1281. ; Y. Hou, H. Wu, H. Yu, Z. Hu, J. Wang, Y. Wu, Angew. Chem. Int. Ed. 2021, 60, 25302-25306. ; Y. Hou, H. Li, H. Wu, H. Yu, Z. Hu, J. Wang, Y. Wu, Dalton Trans. 2022, 51, 14036-14040. ; P. J. Green, G. L. Gard, Inorg. Nucl. Chem. Lett. 1978, 14, 179-182. ; S. D. Brown, P. J. Green, G. L. Gard, J. 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Grant Information: 2016-04561 Natural Sciences and Engineering Research Council of Canada Contributed Indexing: Keywords: Raman spectroscopy; X-ray crystallography; chromium(VI) oxyfluoro-dianions; hyper-valent compounds; quantum-chemical calculations; xenon(VI) chemistry; σ-hole bonds Entry Date(s): Date Created: 20231017 Latest Revision: 20240216 Update Code: 20240216

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