Ligand influence on intramolecular cyclometalation in bis(phosphinimine) rare earth alkyl complexes
Bibliographic record
Abstract
The synthesis and reactivity of two new bis(phosphinimine)carbazole ligands (PippN=PMe 2 ) 2 DMC (HL A , 3) and (PippN=P(C 4 H 8 )) 2 DMC (HL B , 10), where Pipp = para-isopropylphenyl and DMC = 3,6-dimethylcarbazole, are reported. Dialkyl lutetium complexes of 3 and 10 were prepared in the presence of DMAP and THF by reaction of the proteo ligands with the new trialkyl reagent, Lu(CH 2 SiMe 3 ) 3 (DMAP) 2 (4) as well as Lu(CH 2 SiMe 3 ) 3 (THF) 2 . For both ligands 3 and 10, the resulting lutetium complexes were prone to intramolecular cyclometalative alkane elimination reactions whereby the location of cyclometalation was influenced by the identity of the ancillary ligand coordinated to the metal. For ligand 3, cyclometalation of two PMe 2 groups generated the complex (L A -κ 3 N,κ 2 C)Lu(DMAP) 2 (5), whereas ligand 10 resulted in the single ortho-metalation of a para-isopropylphenyl ring to afford (L B -κ 3 N,κC)Lu(CH 2 SiMe 3 ) (12). When complexed with scandium, ligand 10 behaved differently; double cyclometalation of two phospholane moieties resulted in the species (L B -κ 3 N,κ 2 C)Sc (15). The nature of the cyclometalation reactivity of ligands 3 and 10 is supported by X-ray crystallography and kinetic analysis, respectively.
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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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.003 | 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".