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 [WF 4 (L) 4 ] + (L=C 5 H 5 N, P(CH 3 ) 3 ). The [WF 4 (NC 5 H 5 ) 4 ] + cation is synthesised as its [O 3 SCF 3 ] − salt upon reaction of WF 5 (NC 5 H 5 ) 2 with [(CH 3 ) 3 Si(NC 5 H 5 )][O 3 SCF 3 ] in excess C 5 H 5 N, whereas [WF 4 {P(CH 3 ) 3 } 4 ] + is accessed directly from WF 6 upon reaction with (CH 3 ) 3 SiO 3 SCF 3 and excess P(CH 3 ) 3 . These salts were characterised by X‐ray crystallography and Raman spectroscopy in the solid state. New geometry indices for octacoordinate complexes (τ 8 and τ 8 ′) are introduced, allowing for the facile differentiation of trigonal‐dodecahedral (TD) and square‐antiprismatic (SA) geometries. This has disambiguated the SA geometries of [WF 4 (L) 4 ] + and the geometries of a series of previously reported d 0 and d 1 MA 4 B 4 complexes. Computational (DFT−B3LYP) studies of [WF 4 (PH 3 ) 4 ] 2+/+ and related model systems demonstrate the occurrence of a second‐order Jahn‐Teller (SOJT) distortion from TD in d 0 complexes to SA in d 1 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 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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.002 |
| 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 teacher head, 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".