Ethylene Polymerization Using β-Diketimine Complexes of Zirconium
Bibliographic record
Abstract
Ethylene polymerizations were conducted using β-diketimine complexes of Zr [LZrX 3 ( 1 ) and L 2 ZrX 2 ( 2 ) with L = MeC(NAr)CHC(NAr)Me and X = Cl, R (R = Me, Bn)] as well as Cp(L)ZrX 2 ( 3 ) in the presence of MAO. Complexes 1 possess low polymerization activities (ca. 10 5 g PE/(mol Zr h)) and provide PEs with a trimodal, molecular weight distribution. Both 2 and 3 behave as single-site catalysts under these conditions, with the activity of the latter being considerably higher than the former (ca. 10 6 −10 7 vs 10 5 g PE/(mol Zr h)). Induction periods of 10−20 min at 70 °C were observed in polymerizations involving 3 (Ar = Ph, X = Cl, Me) when activated by MAO. The use of [Ph 3 C][B(C 6 F 5 ) 4 ] and 3b (Ar = Ph, X = Me) in the presence of small amounts of MAO (ca. 100:1 Al:Zr) led to rapid monomer uptake and an increase in catalytic activity by about a factor of 4. Lower activities were observed in the presence of Me 3 Al or i Bu 3 Al. Little or no polymerization activity was observed when excess 3b was used as a scrubbing agent (in the presence of [Ph 3 C][B(C 6 F 5 ) 4 ]), and rapid loss of activity was observed when excess 3b was added to a catalyst system already producing PE. Complex 3b reacts with [Ph 3 C][B(C 6 F 5 ) 4 ] in chlorobenzene- d 5 solution at 25 °C to provide [Cp(L)ZrMe][B(C 6 F 5 ) 4 ] ( 4 ). Complex 4 is transformed on heating in chlorobenzene to a dicationic (μ-Cl) 2 complex [(Cp(L)ZrCl) 2 ][B(C 6 F 5 ) 4 ] 2 ( 5 ), which was characterized by X-ray crystallography. Complex 4 forms dinuclear complexes with 3b or Me 3 Al in solution at room temperature. These complexes, [Cp(L)Zr(μ-Me) 2 AlMe 2 ][B(C 6 F 5 ) 4 ] ( 6 ) or [(Cp(L)ZrMe) 2 (μ-Me)][B(C 6 F 5 ) 4 ] ( 7 ), are fluxional in solution; at lower temperature, the solution NMR spectra are consistent with the structures shown. Complex 3b is a potent inhibitor of ethylene polymerization by 4, forming 7, which is resistant to dissociation. The presence of AlMe 3 (or MAO) appears to reversibly displace 3b from 7, allowing the reaction of 3b with [Ph 3 C][B(C 6 F 5 ) 4 ] to proceed to completion.
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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) | 0.001 | 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) | 0.001 | 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".