Origin of Stability and Inhibition of Cooperative Alkyne Hydrofunctionalization Catalysts
Bibliographic record
Abstract
Abstract New entries to the [Ru(Cp/Cp*)(P R 2 N R′ 2 )(MeCN)]PF 6 catalyst family were synthesized, including a Cp complex (R=Cy; R′=Ph) and two Cp* complexes (R=Cy, Ph; R′=Ph). These and other derivatives were used for the intramolecular hydroamination of 2‐ethynylaniline to elucidate trends in catalytic lifetime and rate. The readily accessible [Ru(Cp)(P Cy 2 N Ph 2 )(MeCN)]PF 6 derivative showed comparable lifetime to [Ru(Cp)(P t −Bu 2 N Ph 2 )(MeCN)]PF 6 , the previous optimal catalyst. Donor‐free ‘active’ catalysts, [Ru(Cp/Cp*)(P Cy 2 N Ph 2 )]PF 6 , were prepared and their thermal stability was assessed. The relatively high stability of the Cp derivative was explained by the capacity of the P Cy 2 N Ph 2 ligand to coordinate in a κ 3 ‐(P,P,Ar) mode, which protects the low‐coordinate species. This coordination mode is inaccessible with the Cp* derivative. Additionally, [Ru(Cp*)(P Cy 2 N Ph 2 )]PF 6 readily activated the C−Cl bond of the solvent dichloromethane. Variable time normalization analysis (VTNA) revealed that the indole product inhibited the catalyst [Ru(Cp)(P Cy 2 N Ph 2 )(MeCN)]PF 6 , which slowed catalytic rates.
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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 | 0.001 |
| 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".