[H(OXeF<sub>2</sub>)<sub><i>n</i></sub>][AsF<sub>6</sub>] and [FXe<sup>II</sup>(OXe<sup>IV</sup>F<sub>2</sub>)<sub><i>n</i></sub>][AsF<sub>6</sub>] (<i>n</i> = 1, 2): Examples of Xenon(IV) Hydroxide Fluoride and Oxide Fluoride Cations and the Crystal Structures of [F<sub>3</sub>Xe---FH][Sb<sub>2</sub>F<sub>11</sub>] and [H<sub>5</sub>F<sub>4</sub>][SbF<sub>6</sub>]·2[F<sub>3</sub>Xe---FH][Sb<sub>2</sub>F<sub>11</sub>]
Bibliographic record
Abstract
The xenon(IV) hydroxide fluoride and oxide fluoride salts, [H(OXeF2)n][AsF6] and [FXe(II)(OXe(IV)F2)n][AsF6] (n = 1, 2), have been synthesized as the natural abundance and the (18)O- and (2)H-enriched salts and structurally characterized by low-temperature Raman spectroscopy. Quantum-chemical calculations have been used to arrive at vibrational assignments. The experimental vibrational frequencies and isotopic shift trends are reproduced by the calculated gas-phase frequencies at several levels of theory. The cation chain is limited to one or two OXeF2 subunits, which are oxygen-bridged and strongly ion-paired with the AsF6(-) anion. The reaction of XeOF2·xHF with a superacidic HF/SbF5 solvent mixture yielded crystals of [H5F4][SbF6]·2[XeF3·HF][Sb2F11], [XeF3·HF][Sb2F11], and [XeF3][SbF6]. The XeF3(+) cations of each salt are very similar, displaying T-shaped primary coordination of xenon to three fluorine atoms (AX3E2 VSEPR arrangement) and a secondary contact to the fluorine atom of HF in [H5F4][SbF6]·2[XeF3·HF][Sb2F11] and [XeF3·HF][Sb2F11] or to a fluorine atom of SbF6(-) in [XeF3][SbF6]. The secondary coordination spheres of xenon in [H5F4][SbF6]·2[XeF3·HF][Sb2F11] and [XeF3·HF][Sb2F11] are similar; however, the F3Xe---FH(+) cation of the latter salt is disordered. An additional contact between the XeF3(+) cation and the SbF6(-) anion in [H5F4][SbF6]·2[XeF3·HF][Sb2F11] presumably alters the crystal packing sufficiently to give an ordered F3Xe---FH(+) cation, a rare example in which HF is coordinated to a noble gas. The latter compound also provides the first documentation of the H5F4(+) acidium ion, which forms a zigzag F4-chain terminated by SbF6(-) anions. Enthalpies and Gibbs free energies of reaction obtained from Born-Fajans-Haber thermochemical cycles support the proposed decomposition pathways.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
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".