XeF<sub>2</sub>Coordination to a Halogen Center; Raman Spectra (<i>n</i>= 1, 2) and X-ray Crystal Structures (<i>n</i>= 2) of [BrOF<sub>2</sub>][AsF<sub>6</sub>]·<i>n</i>XeF<sub>2</sub>and [XOF<sub>2</sub>][AsF<sub>6</sub>] (X = Cl, Br)
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Bibliographic record
Abstract
The syntheses and structural characterizations of the [XOF(2)][AsF(6)] (X = Cl, Br) salts and the XeF(2) adduct-salts, [BrOF(2)][AsF(6)].nXeF(2) (n = 1, 2), are described. Although the [XOF(2)][AsF(6)] salts have been known for some time, their crystal structures had not been reported until the present study. The crystal structure of [BrOF(2)][AsF(6)] shows a positional disorder among the oxygen atom and the fluorine atoms. Both ClOF(2)(+) and BrOF(2)(+) have pseudo-octahedral coordination with a primary tripodal coordination sphere consisting of an oxygen atom and two fluorine atoms and a secondary coordination sphere consisting of three long contacts to fluorine atoms of different AsF(6)(-) anions. The low-temperature Raman spectra of [XOF(2)][AsF(6)] have been assigned on the basis of the crystal structures and with the aid of quantum-chemical calculations using [XOF(2)][AsF(6)](3)(2-) as a model for the crystallographic environment of XOF(2)(+). Several examples of XeF(2) coordinated through fluorine to transition metal centers are known, but no crystallographically characterized examples of XeF(2) coordinated to a nonmetal center other than xenon are known. The complex cation salts, [BrOF(2)][AsF(6)].nXeF(2) (n = 1, 2), were synthesized, and their Raman spectra have been assigned with the aid of quantum-chemical calculations. Although the structure of [BrOF(2)][AsF(6)].2XeF(2) is similar to that of the recently reported krypton analogue, notable differences occur. The contact distances between bromine and the fluorine atoms of NgF(2) (Ng = Kr, Xe) are shorter in [BrOF(2)][AsF(6)].2XeF(2) than in the KrF(2) analogue, which is attributed to the more polar natures of the Xe-F bonds. Unlike [BrOF(2)][AsF(6)].2KrF(2), which has been shown in the prior study to be stable in HF solution at room temperature, [BrOF(2)][AsF(6)].2XeF(2) enters into a dissociative equilibrium in which fluoride ion abstraction by BrOF(2)(+) occurs to give Xe(2)F(3)(+) and BrOF(3). The ELF and QTAIM analyses of [BrOF(2)][AsF(6)](3)(2-) and [BrOF(2)][AsF(6)].2XeF(2) were carried out and are compared with those of [BrOF(2)][AsF(6)].2KrF(2) and for free BrOF(2)(+) to better understand the effect of Br(V) coordination number on the localization domain of the Br(V) valence electron lone pair.
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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 | 0.002 | 0.001 |
| Meta-epidemiology (narrow) | 0.006 | 0.006 |
| Meta-epidemiology (broad) | 0.005 | 0.002 |
| Bibliometrics | 0.001 | 0.003 |
| Science and technology studies | 0.002 | 0.003 |
| Scholarly communication | 0.002 | 0.002 |
| Open science | 0.004 | 0.003 |
| Research integrity | 0.006 | 0.008 |
| 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 it