Unusual Reactivity of a Tm-Pyrrolide/Aluminate Complex with a Metallocene-Type Structural Motif
Bibliographic record
Abstract
Reaction of in situ generated (Me 4 Al) 3 Tm with 2,3,4,5-tetramethylpyrrole afforded Tm(Me){μ-CH 2 AlMe 2 (η 5 -NC 4 Me 4 )] 2 } ( 1 ), containing a terminally bonded CH 3 group. The two pyrrolide rings confer the bent-metallocenic motif to the lanthanide by adopting a fairly symmetrical π-bonding mode. Each of the N atoms of the pyrrolide rings is bonded to one AlMe 2 residue, which in turn bridges the lanthanide through a CH 2 unit of an Al 2 (μ-CH 2 )Tm moiety. The reactivity of the terminal Me group of 1 was examined with both H 2 and PhSiH 3 . Reaction with H 2 under high pressure and room temperature caused loss of the terminal methyl group and major redistribution of the pyrrolyl moieties, yielding Tm[AlMe 2 (η 5 -NC 4 Me 4 ) 2 ][(μ-Me)(AlMe 2 )][(μ 3 -CH 2 )(AlMe 3 )] ( 2 ), with a stable ansa -metallocene type of structure and intacting Al 2 (μ-CH 2 )Tm unit. Reaction of 1 with PhSiH 3 under mild conditions afforded an even more complex transformation accompanied by evolution of CH 4 and formation of toluene. The resulting Tm[AlMe 2 (η 5 -NC 4 Me 4 ) 2 ](AlMe 3 )(μ 3 -CH 2 )(μ 3 -SiH 3 )(AlMe 2 )[Al Me 2 (NC 4 Me 4 )] ( 3 ) complex provides a rare example of SiH 3 unit trapping.
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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) | 0.001 | 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) | 0.019 | 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".