Kinetic and Mechanistic Investigation of Metallacycle Ring Opening in an Ortho-Metalated Lutetium Aryl Complex
Bibliographic record
Abstract
Reactivity involving metallacycle ring opening of ortho-metalated bis(phosphinimine)carbazolide complexes ( L Ph -κ 3 N,κ 2 C P-Ph )Lu(THF) ( 1a ) and ( L Pipp -κ 3 N,κ 2 C P-Ph )Lu(THF) ( 1b ); L = [1,8-(Ph 2 P═NAr) 2 dmc]; Ar = Ph ( L Ph ), p -isopropylphenyl ( L Pipp ); dmc = 3,6-dimethylcarbazolide) is described. Reaction of 1a, b with bulky anilines (2,4,6-trimethylaniline, MesNH 2; 2,4,6-triisopropylaniline, TripNH 2 ) promoted metallacycle ring opening of two ortho-metalated P-phenyl groups to liberate the bis(anilide) products ( L Ph -κ 3 N )Lu(NHMes) 2 ( 2 ) and ( L Pipp -κ 3 N )Lu(NHTrip) 2 ( 3 ). Regardless of the quantity of TripNH 2 or MesNH 2 utilized, double ring opening always prevailed to afford the bis(anilide) product, rather than the mono(anilide). In contrast, reaction of complex 1b with the bulkier reagent 2,4,6-tri- tert -butylaniline (Mes*NH 2 ) only caused metallacycle ring opening of one ortho-metalated P-phenyl group, affording the mono(anilide) complex ( L Pipp -κ 3 N,κ C P-Ph )Lu(NHMes*) ( 4 ) exclusively. Complex 4 rapidly undergoes an intramolecular rearrangement whereby metalation of an N-aryl group promotes metallacycle ring opening of the ligated P-phenyl moiety to give ( L Pipp -κ 3 N,κ C N-Pipp )Lu(NHMes*) ( 5 ) as the structural isomer. Through deuterium labeling and kinetic studies it was established that the thermal rearrangement of 4 does not proceed through an imido intermediate. Compounds 2, 3, and 5 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) | 0.000 | 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) | 0.004 | 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".