Competitive Isomerization and Catalyst Decomposition During Ring-Closing Metathesis
Bibliographic record
Abstract
Ring-closing metathesis (RCM) is an elegant means of forming cyclic structural elements in both simple and complex molecules. Mechanistically, the reaction cycle is well understood, though subtle details concerning the fate of the catalyst and the appearance of yield-reducing by-products remain to be fully deciphered. We applied real-time analysis using electrospray ionization mass spectrometry (ESI-MS) to probe the RCM reaction, including studying the dynamics of all charged species in the reaction mixture and investigating the nature of the by-products formed. The catalyst of choice was Grubbs’ second-generation catalyst. The principal findings included the fact that for slower reactions, by-products appeared that differed in mass from the starting material and product by increments of CH2; that isomerization reactions were responsible for these by-products; and that the catalyst decomposes to form charged products including [ClPCy3]+, [HPCy3]+, and the imidazolinium salt of the N-heterocyclic carbene (NHC) ligand. In cases where RCM is slow, isomerization reactions play a disproportionate part in affecting yield of the desired product.
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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 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 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 | 0.001 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 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".