Challenging Metathesis Catalysts with Nucleophiles and Brønsted Base: Examining the Stability of State-of-the-Art Ruthenium Carbene Catalysts to Attack by Amines
Bibliographic record
Abstract
Abstract Critical to advancing the uptake of olefin metathesis in leading contexts, including pharmaceutical manufacturing, is identification of highly active catalysts that resist decomposition. Amines constitute an aggressive challenge to ruthenium metathesis catalysts. Examined here is the impact of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), morpholine, n-butylamine, and triethylamine on Ru metathesis catalysts that represent the current state of the art, including cyclic alkyl amino carbene (CAAC) and N-heterocyclic carbene (NHC) complexes. Accordingly, the amine-tolerance of the nitro-Grela catalyst RuCl2(H2IMes)(═CHAr) (nG; Ar = C6H4-2-OiPr-5-NO2) is compared with that of its CAAC analogues nGC1 and nGC2, and the Hoveyda-class catalyst RuCl2(C2)(═CHAr′) HC2 (Ar′ = C6H4-2-OiPr). In C1, the carbene carbon is flanked by an N-2,6-Et2C6H3 group and a CMePh quaternary carbon; in C2, by an N-2-iPr-6-MeC6H3 group and a CMe2 quaternary carbon. The impact of 1 equiv amine per Ru on turnover numbers (TONs) in ring-closing metathesis of diethyl diallylmalonate was assessed at 9 ppm Ru, at RT and 70 °C. The deleterious impact of amines followed the trend NEt3 ∼ NH2nBu ≪ DBU ∼ morpholine. Morpholine is shown to decompose nGC1 by nucleophilic abstraction of the methylidene ligand; DBU, by proton abstraction from the metallacyclobutane. Decomposition was minimized at 70 °C, at which nGC1 enabled TONs of ca. 60 000 even in the presence of morpholine or DBU, vs ca. 80 000 in the absence of base. Unexpectedly, H2IMes catalyst nG delivered 70–90% of the performance of nGC1 at high temperatures, and underwent decomposition by Brønsted base at a similar rate. Density functional theory (DFT) analysis shows that this similarity is due to comparable net electron donation by the H2IMes and C1 ligands. Catalysts bearing the smaller C2 ligand were comparatively insensitive to amines, owing to rapid, preferential bimolecular decomposition.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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 | 0.001 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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 source (direct Gemma or distilled Codex), 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".