Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF <sub>5</sub> ] <sup>+</sup> and [Xe <sub>2</sub> F <sub>11</sub> ] <sup>+</sup> Salts of the [Cr <sup>VI</sup> OF <sub>5</sub> ] <sup>−</sup> , [Cr <sup>V</sup> OF <sub>5</sub> ] <sup>2−</sup> , [Cr <sup>V</sup> <sub>2</sub> O <sub>2</sub> F <sub>8</sub> ] <sup>2−</sup> , and [Cr <sup>IV</sup> F <sub>6</sub> ] <sup>2−</sup> Anions
Bibliographic record
Abstract
Abstract Molten mixtures of XeF 6 and Cr VI OF 4 react by means of F 2 elimination to form [XeF 5 ][Xe 2 F 11 ][Cr V OF 5 ] ⋅ 2 Cr VI OF 4 , [XeF 5 ] 2 [Cr IV F 6 ] ⋅ 2 Cr VI OF 4 , [Xe 2 F 11 ] 2 [Cr IV F 6 ], and [XeF 5 ] 2 [Cr V 2 O 2 F 8 ], whereas their reactions in anhydrous hydrogen fluoride (aHF) and CFCl 3 /aHF yield [XeF 5 ] 2 [Cr V 2 O 2 F 8 ] ⋅ 2 HF and [XeF 5 ] 2 [Cr V 2 O 2 F 8 ] ⋅ 2 XeOF 4 . Other than [Xe 2 F 11 ][M VI OF 5 ] and [XeF 5 ][M VI 2 O 2 F 9 ] (M=Mo or W), these salts are the only Group 6 oxyfluoro‐anions known to stabilize noble‐gas cations. Their reaction pathways involve redox transformations that give [XeF 5 ] + and/or [Xe 2 F 11 ] + salts of the known [Cr V OF 5 ] 2− and [Cr IV F 6 ] 2− anions, and the novel [Cr V 2 O 2 F 8 ] 2− anion. A low‐temperature Raman spectroscopic study of an equimolar mixture of solid XeF 6 and CrOF 4 revealed that [Xe 2 F 11 ][Cr VI OF 5 ] is formed as a reaction intermediate. The salts were structurally characterized by LT single‐crystal X‐ray diffraction and LT Raman spectroscopy, and provide the first structural characterizations of the [Cr V OF 5 ] 2− and [Cr V 2 O 2 F 8 ] 2− anions, where [Cr V 2 O 2 F 8 ] 2− represents a new structural motif among the known oxyfluoro‐anions of Group 6. The X‐ray structures show that [XeF 5 ] + and [Xe 2 F 11 ] + form ion pairs with their respective anions by means of Xe‐ ‐ ‐F–Cr bridges. Quantum‐chemical calculations were carried out to obtain the energy‐minimized, gas‐phase geometries and the vibrational frequencies of the anions and their ion pairs and to aid in the assignments of their Raman spectra.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.020 | 0.009 |
| Meta-epidemiology (narrow) | 0.025 | 0.024 |
| Meta-epidemiology (broad) | 0.023 | 0.013 |
| Bibliometrics | 0.009 | 0.019 |
| Science and technology studies | 0.014 | 0.016 |
| Scholarly communication | 0.008 | 0.013 |
| Open science | 0.021 | 0.014 |
| Research integrity | 0.014 | 0.036 |
| Insufficient payload (model declined to judge) | 0.001 | 0.003 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; both teacher heads agree on what is shown here.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".