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 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 | 0.001 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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".