Preparation, Structural Analysis, and Reactivity Studies of Phosphenium Dications
Bibliographic record
Abstract
This work expands on the recent synthesis and reactivity of the two-coordinate P(III)-containing dication [((Ph 3 P) 2 C)P(N i Pr 2 )] 2+ ( 3a 2+ ). Two additional dications of general formula [((RPh 2 P) 2 C)P(NR′ 2 )] 2+ ( 3b 2+, R = 1/2 (CH 2 ) 3, R′ = i Pr; 3c 2+, R = Ph, R′ = Cy) have been prepared. Solution and solid-state 31 P NMR isotropic shifts for this dication class were observed around 360 ppm. Except for [ 3a ][SbF 6 ] 2, the 31 P CP/MAS NMR spectra reveal a high degree of structural disorder around the dicationic site in the solid state. Surprisingly, the synthesis of dication 3a 2+ was only possible in the presence of AlCl 4 –, SbF 6 –, and substituted tetraarylborates, while the use of ClO 4 –, OTf –, BF 4 –, PF 6 –, and BPh 4 – resulted in complex product mixtures. Single-crystal X-ray analysis of dications 3a 2+ and 3c 2+ suggested a 4π allyl-like structure for the central CPN fragment, and this has been supported through detailed theoretical investigations. Initial reactivity studies between dications 3a 2+ / 3c 2+ and PMe 3 show an equilibrium between the free dication and the target adduct. Furthermore, 3a 2+ has been shown to be capable of O–H bond activation using water and methanol and polymerizes THF when it is dissolved in this solvent.
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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 | 0.001 |
| 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".