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 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 | 0.001 | 0.000 |
| Research integrity | 0.001 | 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".