Reactivity of Scandium β-Diketiminate Alkyl Complexes with Carbon Dioxide
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Bibliographic record
Abstract
The reactions of two highly air- and moisture-sensitive scandium bis(alkyls) supported by a bulky β-diketiminato (nacnac) ligand with carbon dioxide are described. [κ 2 -ArNC( t Bu)CHC( t Bu)NAr]ScR 2 (Ar = 2,6- i Pr 2 C 6 H 3; R = CH 3, 1a; R = CH 2 SiMe 3, 1b ) react rapidly with CO 2 to give mixtures of mono- and bis(carboxylato) insertion products 2a / 2b and 3a / 3b depending on the stoichiometry and conditions of the reaction. Compound 2a (R = CH 3 ) is a dimeric complex with bridging acetato groups, as determined by X-ray crystallography. These compounds were characterized by NMR spectroscopy, and 3a could be isolated in pure form. Treatment of these compounds with excess CO 2 resulted in addition to the central carbon of the Sc(nacnac) six-membered ring and displacement of the nitrogen donors to yield dimeric scandium carboxylates 4a / 4b; compound 4b was characterized by X-ray crystallography. Reactions of the nacnac scandium cations formed upon abstraction of one or two methides from 1a using B(C 6 F 5 ) 3 with CO 2 were also explored. Although the products were qualitatively more thermally robust, eventually ligand displacement occurred in these cationic acetato complexes as well. Nevertheless, insertion products were characterizable in solution using NMR spectroscopy. Overall, this study shows the facility with which CO 2 is taken up by scandium alkyls but that the nacnac ligand framework is too reactive to support chemistry aimed at catalytic conversion of CO 2 into other products.
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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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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) | 0.000 | 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 it