Synthesis and Structural Characterization of the First Thermally Stable, Neutral, and Electrophilic Phosphinidene Complexes of Vanadium
Bibliographic record
Abstract
The first thermally stable, neutral, electrophilic phosphinidene complexes of vanadium, [CpV(CO) 3 {η 1 -P(NR 2 )}] (R = i Pr ( 3a ), Cy ( 3b )), have been prepared by the reaction of [Na] 2 [CpV(CO) 3 ] with Cl 2 PNR 2 . The molecules 3a and 3b have been characterized by microanalysis, IR, and 1 H and 31 P{ 1 H} NMR spectroscopy, and for 3a also by single-crystal X-ray diffraction. The structure of 3a exhibits a piano stool geometry closely related to that of CpV(CO) 4 with an η 1 -phosphinidene ligand replacing CO in one of the basal coordination sites of the vanadium atom (V(1)−P(1) = 2.300(2) Å). The reactivity of 3a toward a variety of unsaturated substrates: PhC≡CPh, di- t Bu-imidazol-2-ydene, PhN 3, and Ph 2 C═N═N has been examined to probe the electrophilic (or nucleophilic) character of the low-coordinate P(I) site. In all cases reactions occur exclusively at the phosphinidene phosphorus atom, without CO displacement, affording examples of P-coordinated phosphirene [CpV(CO) 3 {P(N i Pr 2 )CPh═CPh}] ( 7 ), abnormal NCN carbene adduct [CpV(CO) 3 {P(N i Pr 2 )-4-cyclo-C 3 H 2 -1,3-(N t Bu) 2 )}] ( 8 ), diazaphosphaimine [CpV(CO) 3 {P(N i Pr 2 )═N−N═CPh 2 }] ( 12 ), and P-coordinated phosphaimine [CpV(CO) 3 {P(N i Pr 2 )═NPh}] ( 14 ) complexes. The η 1 -phosphaimine complexes 12 and 14 lose carbon monoxide to yield derivatives [CpV(CO) 2 {P(N i Pr 2 )N−N═CPh 2 }] ( 9 ) and [CpV(CO) 2 {P(N i Pr 2 )═NPh}] ( 15 ), which contain η 2 -(P,N)-coordinated phosphaimine ligands. An η 3 -(P,N,N)-bound phosphaimine ligand is present in an isomer of 9, namely, [CpV(CO) 2 {P(N i Pr 2 )N−N═CPh 2 }], 13 . Complexes 3a, 7, 8, 9, 14, and 15 have been characterized by X-ray crystallography.
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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 | 0.000 | 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) | 0.006 | 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".