Synthesis and Reactivity of Dialkyl Lutetium Complexes Supported by a Novel Bis(phosphinimine)carbazole Pincer Ligand
Bibliographic record
Abstract
The synthesis of a novel bis(phosphinimine) ancillary ligand based on a carbazole framework is described (H L Ph, 4a; H L Pipp, 4b; Ph = phenyl, Pipp = para -isopropylphenyl). Protonolysis with Lu(CH 2 SiMe 3 ) 3 (THF) 2 afforded the corresponding lutetium dialkyl complexes (Lu L Ph (CH 2 SiMe 3 ) 2, 5a; Lu L Pipp (CH 2 SiMe 3 ) 2, 5b ), which were thermally sensitive and rapidly underwent intramolecular metalative alkane elimination to generate Lu L Ph* (CH 2 SiMe 3 )(THF), 6a, and Lu L Pipp* (CH 2 SiMe 3 )(THF), 6b, as highly reactive intermediates. Complexes 6a and 6b further decomposed, cleanly generating doubly metalated complexes Lu L Ph** (THF), 7a, and Lu L Pipp** (THF), 7b, respectively, as the thermodynamic products. Kinetic analysis of the decomposition of 5a revealed a first-order mechanism with activation parameters Δ H ⧧ = 19.2(1) kcal·mol −1 and Δ S ⧧ = −8.2(2) cal·K −1 ·mol −1 . Compounds 4a, 4b, 6b, and 7b were characterized by single-crystal X-ray diffraction studies.
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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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.007 | 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".