On the Reactivity of F<sub>3</sub>S≡NXeF<sup>+</sup>: Syntheses and Structural Characterizations of [F<sub>4</sub>S═N−Xe---N≡SF<sub>3</sub>][AsF<sub>6</sub>], a Rare Example of a N−Xe−N Linkage, and [F<sub>3</sub>S(N≡SF<sub>3</sub>)<sub>2</sub>][AsF<sub>6</sub>]
Bibliographic record
Abstract
The F(4)S=N-Xe---N[triple bond]SF(3)(+) cation has been synthesized as the AsF(6)(-) salt by rearrangement of [F(3)S[triple bond]NXeF][AsF(6)] in N[triple bond]SF(3) solvent at 0 degrees C. Deep yellow [F(4)S=N-Xe---N[triple bond]SF(3)][AsF(6)], which crystallized from a N[triple bond]SF(3) solution at -10 degrees C, was characterized by Raman spectroscopy (-160 degrees C) and by single-crystal X-ray diffraction (-173 degrees C). The Xe-N bond length (2.079(3) A) of the F(4)S=N-Xe---N[triple bond]SF(3)(+) cation is among the shortest Xe-N bonds presently known. The F(4)S=NXe(+) cation interacts with N[triple bond]SF(3) by means of a Xe---N donor-acceptor bond (2.583(3) A) that is significantly longer than the primary Xe-N bond (2.079(3)A) but significantly shorter than the sum of the Xe and N van der Waals radii (3.71 A). The F(4)S=N-Xe---N[triple bond]SF(3)(+) cation undergoes a redox decomposition in N[triple bond]SF(3) at 0 degrees C, forming [F(3)S(N[triple bond]SF(3))(2)][AsF(6)], cis-N(2)F(2), and Xe, which were characterized by low-temperature Raman spectroscopy in the solid state and by (19)F NMR spectroscopy in N[triple bond]SF(3) solvent (0 degrees C). Colorless [F(3)S(N[triple bond]SF(3))(2)][AsF(6)] crystallized from N[triple bond]SF(3) at -10 degrees C and was characterized by low-temperature, single-crystal X-ray diffraction. The S(IV) atom of F(3)S(N[triple bond]SF(3))(2)(+) has long contacts with the N atoms of two N[triple bond]SF(3) molecules and a F ligand of a neighboring AsF(6)(-) anion. The arrangement of long contacts avoids, to the maximum extent, the F atoms of SF(3)(+) and the nonbonding electron pair situated on the pseudo-3-fold axis opposite the F ligands of SF(3)(+), providing distorted octahedral coordination about the S(IV) atom. Quantum-chemical calculations using MP2, B3LYP, and PBE1PBE methods were employed to arrive at the gas-phase geometries, charges, bond orders, valencies, and vibrational frequencies for F(4)S=N-Xe---N[triple bond]SF(3)(+) and F(3)S(N[triple bond]SF(3))(2)(+) to aid in the assignments of experimental vibrational frequencies. The F(4)S=N-Xe---N[triple bond]SF(3)(+) cation expands the known chemistry of the F(4)S=N- group and is the first example of a N-Xe-N linkage to be structurally characterized by single-crystal X-ray diffraction.
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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) | 0.001 | 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".