Zirconium Complexes of a Cross-Bridged Cyclam
Bibliographic record
Abstract
The acid−base reaction of tetrabenzylzirconium with 1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (H 2 (CBC), 1 ) produces (CBC)Zr(CH 2 Ph) 2, 2 . Similarly, reaction of 2 with phenols yields (CBC)Zr(CH 2 Ph)(O-2,6-C 6 H 3 Bu t 2 ), 3, and (CBC)Zr(O-2,6-C 6 H 3 Me 2 ) 2, 5 . Prolonged heating of 3 leads to the metalated product (CBC)Zr[κ 2 (C,O)-OC 6 H 3 (6-Bu t )(2-CMe 2 CH 2 )], 4 . Reaction of ZrCl 2 [N(SiMe 3 ) 2 ] 2 with H 2 (CBC) leads to (CBC)ZrCl 2, 6, which subsequently affords (CBC)Zr(X)(Y) by salt metathesis ( 7, X = Cl, Y = N(SiMe 3 ) 2; 8, X = Y = CH 3; 9, X = Y = CH 2 Si(CH 3 ) 3 ). Compounds 3 and 7 show restricted rotation about the Zr−O and Zr−N bonds, respectively, on the NMR time scale. For 3, the energy of activation for this process was determined to be 69 ± 1 kJ/mol. Neither 6 nor 8 shows ethylene polymerization activity when treated with 500 equiv of MAO. Reaction of 6 with 2 equiv of n-BuLi in the presence of excess diphenylacetylene leads to the zirconacyclopentadiene 10, (CBC)Zr(C 4 Ph 4 ). The structures of 5, 9, and 10 have been determined by X-ray crystallography, and all three display distorted octahedral geometry.
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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 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.043 | 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".