Reactivity of Terminal Electrophilic Phosphinidene Complexes: Synthesis of the First Rhenium Phosphinidene, [Re(CO)<sub>5</sub>(η<sup>1</sup>-PN<i><sup>i</sup></i>Pr<sub>2</sub>)][AlCl<sub>4</sub>], and Novel Reactions with Azobenzene
Bibliographic record
Abstract
The first terminal rhenium phosphinidene complex, [Re(CO) 5 (η 1 -PN i Pr 2 )][AlCl 4 ], has been synthesized by chloride abstraction from [Re(CO) 5 {P(Cl)(N i Pr 2 )}]. The electrophilic character of the terminal phosphinidene ligand is demonstrated by phosphine addition at the unsaturated phosphorus center and by novel reactions with azobenzene, PhN NPh, which generate, via C−H activation and P−N and P−C bond formation, coordinated benzodiazaphosphole ligands. The cations [Re(CO) 5 P(PPh 3 )N i Pr 2 ] + and [Re(CO) 5 {P(PhNNHC 6 H 4 )N i Pr 2 }] + have been crystallographically characterized as their AlCl 4 - salts. The corresponding late-metal terminal phosphinidene complexes [Co(CO) 3 (PR 3 )(η 1 -PN i Pr 2 )][AlCl 4 ] (R = Ph, Et) also afford coordinated benzodiazaphospholes via reaction with PhN NPh.
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 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 | 0.001 |
| Meta-epidemiology (narrow) | 0.002 | 0.002 |
| Meta-epidemiology (broad) | 0.003 | 0.001 |
| Bibliometrics | 0.001 | 0.003 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.001 | 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; both teacher heads agree on what is shown here.
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".