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Record W4387692535 · doi:10.1002/chem.202303059

Chromium(VI) Oxyfluoride Dianions, [Cr<sub>2</sub>O<sub>4</sub>F<sub>6</sub>]<sup>2−</sup> and [CrO<sub>2</sub>F<sub>4</sub>]<sup>2−</sup>; Syntheses and Structures of [XeF<sub>5</sub>]<sub>2</sub>[Cr<sub>2</sub>O<sub>4</sub>F<sub>6</sub>], [XeF<sub>5</sub>]<sub>2</sub>[Cr<sub>2</sub>O<sub>4</sub>F<sub>6</sub>] ⋅ <i>n</i>X (X=HF, <i>n</i>=4; X=XeOF<sub>4</sub>, <i>n</i>=2), and [XeF<sub>5</sub>][Xe<sub>2</sub>F<sub>11</sub>][CrO<sub>2</sub>F<sub>4</sub>]

2023· article· en· W4387692535 on OpenAlexafffund
Mark R. Bortolus, Hélène P. A. Mercier, Gary J. Schrobilgen

Bibliographic record

VenueChemistry - A European Journal · 2023
Typearticle
Languageen
FieldChemistry
TopicInorganic Fluorides and Related Compounds
Canadian institutionsMcMaster University
FundersNatural Sciences and Engineering Research Council of Canada
KeywordsChemistryCrystallographyRaman spectroscopyOctahedronCrystal structureChromiumDimerX-ray crystallographyIonNatural bond orbitalInorganic chemistryPhysical chemistryDensity functional theoryComputational chemistryDiffraction

Abstract

fetched live from OpenAlex

Abstract 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.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame distilled prediction

Teacher imitation

Not 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.

metaresearch head score (Codex)0.036
metaresearch head score (Gemma)0.020
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMetaresearch, Meta-epidemiology (narrow), Meta-epidemiology (broad), Bibliometrics, Science and technology studies, Scholarly communication, Open science, Research integrity, Insufficient payload (model declined to judge)
Consensus categoriesMetaresearch, Meta-epidemiology (narrow), Meta-epidemiology (broad), Bibliometrics, Science and technology studies, Scholarly communication, Open science, Research integrity
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.096
Threshold uncertainty score0.993

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0360.020
Meta-epidemiology (narrow)0.0590.067
Meta-epidemiology (broad)0.0480.031
Bibliometrics0.0250.043
Science and technology studies0.0310.031
Scholarly communication0.0260.026
Open science0.0400.031
Research integrity0.0350.066
Insufficient payload (model declined to judge)0.0010.015

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.

Opus teacher head0.010
GPT teacher head0.204
Teacher spread0.193 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; both teacher heads agree on what is shown here.

Study designBench or experimental
Domainnot available
GenreEmpirical

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".

Quick stats

Citations1
Published2023
Admission routes2
Has abstractyes

Explore more

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