Donor-Induced Decomposition of the Grubbs Catalysts: An Intercepted Intermediate
Why this work is in the frame
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Bibliographic record
Abstract
The σ-alkyl species RuCl 2 (CH 2 PCy 3 )(py) 3 ( 3a ) is intercepted on adding pyridine to the first-generation Grubbs catalyst 1a during RCM or to the isolated resting-state species RuCl 2 (PCy 3 ) 2 (═CH 2 ) ( 2a ). Complex 3a is formed by pyridine-induced displacement of PCy 3 and nucleophilic attack of the liberated PCy 3 on the methylidene carbon. The rapid, near-quantitative conversion of 2a into 3a indicates that nucleophilic attack by PCy 3 is the primary deactivating event. Once formed, 3a decomposes more slowly via several competing pathways. One such pathway involves elimination of the σ-alkyl ligand as [CH 3 PCy 3 ]Cl ( A ), following proton and chloride abstraction. Observation of nearly 80% 3a during RCM by 1a in the presence of pyridine confirms the relevance of this behavior to metathesis and implicates the resting-state methylidene 2a as the vulnerable species, rather than the metallacyclobutane intermediate. Any donor capable of displacing PCy 3 and stabilizing a five-coordinate methylidene adduct is predicted to trigger the same deactivation sequence, steric factors permitting.
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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 | 0.001 |
| 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 | 0.001 | 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 it