Synthesis, Structure, and Insertion Reactivity of Zirconium and Hafnium Amidate Benzyl Complexes
Bibliographic record
Abstract
A series of amidate-ligated dibenzyl zirconium and hafnium complexes are accessed through protonolysis reactions of the amide proligands 2,6-dimethylphenylpivaloylamide, [ DMP (NO) tBu ]H ( 3 ), and 1,3-bis(1-adamantylamide)-2,2-dimethylpropane, Ad [O 2 N 2 ]H 2 ( 5 ), with Zr(CH 2 Ph) 4 or Hf(CH 2 Ph) 4 . The resulting dibenzyl complexes [ DMP (NO) tBu ] 2 Zr(CH 2 Ph) 2 ( 4 ), Ad [O 2 N 2 ]Zr(CH 2 Ph) 2 (THF) ( 6 ), and Ad [O 2 N 2 ]Hf(CH 2 Ph) 2 (THF) ( 7 ) are structurally characterized. Insertion reactions of 4 with isocyanides are investigated, resulting in the formation of an η 2 -iminoacyl species, [ DMP (NO) tBu ] 2 Zr(η 2 -2,6-Me 2 C 6 H 3 N═CCH 2 Ph) 2 ( 8 ), which undergoes thermal C═C coupling to form an enediamido complex, [ DMP (NO) tBu ] 2 Zr(η 4 -ArNC(CH 2 Ph)═C(CH 2 Ph)NAr) (Ar = 2,6-Me 2 C 6 H 3 ) ( 9 ). Analogous insertion of t BuN≡C into the Zr−C bonds of 4 results in the formation of a vinylamido complex, [ DMP (NO) tBu ] 2 Zr(N( t Bu)CH═CHPh) 2 ( 10 ), through a presumed 1,2-hydrogen migration mechanism from an iminoacyl intermediate similar to 8 . Complexes 8 and 9 are also structurally characterized.
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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) | 0.001 | 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) | 0.010 | 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".