Super-High Active, Homogeneous Vanadium(V) Complexes Bearing Bidentate Phenoxy-Phosphine Ligands for Diverse Olefins Copolymerization
Bibliographic record
Abstract
A series of imido-vanadium(V) complexes bearing bidentate phenoxy-phosphine ligands were synthesized and characterized. These complexes demonstrated excellent catalytic performance in ethylene/1-hexene copolymerization, achieving high activities of 12–49 × 10 6 g polymer (mol V ) -1 ·h -1 and affording random copolymers with tunable 1-hexene incorporations. These catalysts also exhibited ultrahigh activity, up to 112.2 × 10 6 g polymer (mol V ) -1 ·h -1 , in ethylene/norbornene (NB) copolymerization, yielding cyclic olefin copolymers with adjustable NB incorporation. Remarkably, these catalysts demonstrate exceptional tolerance toward polar functional group, enabling efficient copolymerization of ethylene with both 10-undecen-1-ol (U-OH) and 5-norbornene-2-methanol (NB-OH), incorporating ~2 mol% polar comonomers with high activity. Different with the catalytic behavior in copolymerization of ethylene with nonpolar comonomers, the activities in E/U-OH copolymerization (25.7 × 10 6 g polymer (mol V ) -1 ·h -1 ) were much higher than those in E/NB-OH copolymerization (8.6 × 10 6 g polymer (mol V ) -1 ·h -1 ). DFT calculations revealed that catalytic performance is governed by synergistic electronic and steric effects. In polar comonomer systems, steric effects emerged as the dominant factor, with NB-OH exhibiting larger buried volume around the vanadium center upon coordination compared to U-OH. This work provides fundamental insights into vanadium-catalyzed copolymerization and offers new strategies for tailored polyolefin design.
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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 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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".