Stabilisation of [W<sup>V</sup>F<sub>4</sub>]<sup>+</sup> by N‐ and P‐Donor Ligands: Second‐Order Jahn‐Teller Effects in Octacoordinate d<sup>1</sup> Complexes
Bibliographic record
Abstract
Abstract The first isolated examples of cationic fluoridotungsten(V) complexes are reported as octacoordinate [WF4(L)4]+ (L=C5H5N, P(CH3)3). The [WF4(NC5H5)4]+ cation is synthesised as its [O3SCF3]− salt upon reaction of WF5(NC5H5)2 with [(CH3)3Si(NC5H5)][O3SCF3] in excess C5H5N, whereas [WF4{P(CH3)3}4]+ is accessed directly from WF6 upon reaction with (CH3)3SiO3SCF3 and excess P(CH3)3. These salts were characterised by X‐ray crystallography and Raman spectroscopy in the solid state. New geometry indices for octacoordinate complexes (τ8 and τ8′) are introduced, allowing for the facile differentiation of trigonal‐dodecahedral (TD) and square‐antiprismatic (SA) geometries. This has disambiguated the SA geometries of [WF4(L)4]+ and the geometries of a series of previously reported d0 and d1 MA4B4 complexes. Computational (DFT−B3LYP) studies of [WF4(PH3)4]2+/+ and related model systems demonstrate the occurrence of a second‐order Jahn‐Teller (SOJT) distortion from TD in d0 complexes to SA in d1 complexes, with the degree of SOJT stabilisation being most significant in 5d complexes containing fluorido ligands and monodentate neutral donors.
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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 | 0.001 | 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".