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
Bibliographic record
Abstract
Molten mixtures of XeF 6 and Cr VI OF 4 in 1:1 and 1:2 molar ratios undergo reduction to Cr(V) and Cr(IV) by means of F 2 elimination to form [XeF 5 ][Xe 2 F 11 ][Cr V OF 5 ]∙2Cr VI OF 4 and [XeF 5 ] 2 [Cr IV F 6 ]∙2Cr VI OF 4 , respectively, as shown by low-temperature (LT) single-crystal X-ray diffraction (SCXRD). A LT Raman spectroscopic study of an equimolar mixture of solid XeF 6 and CrOF 4 and its melt showed that [Cr VI OF 5 ] – is formed as an intermediate. Reaction of [XeF 5 ] 2 [Cr IV F 6 ]∙2Cr VI OF 4 with XeF 6 in a melt gave [Xe 2 F 11 ] 2 [Cr IV F 6 ] and [XeF 5 ] 2 [Cr V 2 O 2 F 8 ]. Their LT crystal structures revealed that [XeF 5 ] + and [Xe 2 F 11 ] + are coordinated to their respective [CrF 6 ] 2− and [Cr 2 O 2 F 8 ] 2− anions by means of Xe---F–Cr bridges to form infinite chain structures. The reactions of a 1:1 molar ratio of XeF 6 and CrOF 4 in anhydrous hydrogen fluoride (aHF) and in mixed CFCl 3 /aHF solvents yielded [XeF 5 ] 2 [Cr V 2 O 2 F 8 ]∙2HF and a mixture of [XeF 5 ] 2 [Cr V 2 O 2 F 8 ]∙2HF and [XeF 5 ] 2 [Cr V 2 O 2 F 8 ]∙2XeOF 4 , respectively. The SCXRD structures of the latter and aforementioned salts provide the first X-ray structures of [CrOF 5 ] 2– and [Cr 2 O 2 F 8 ] 2– . The [XeF 5 ] 2 [Cr V 2 O 2 F 8 ]∙2XeOF 4 and [XeF 5 ][Xe 2 F 11 ][Cr V OF 5 ]∙2Cr VI OF 4 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 [Cr VI OF 5 ] – , [XeF 5 ] 2 [Cr V 2 O 2 F 8 ]∙2XeOF 4 , [Cr V 2 O 2 F 8 ] 2– , [XeF 5 ][Xe 2 F 11 ][Cr V OF 5 ]∙2Cr VI OF 4 , [Cr V OF 5 ] 2– , and to aid in the assignments of their vibrational frequencies.
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.002 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.002 |
| Research integrity | 0.001 | 0.003 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
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".