Transition-Metal-Free Formation of C–E Bonds (E = C, N, O, S) and Formation of C–M Bonds (M = Mn, Mo) from <i>N</i>-Heterocyclic Carbene Mediated Fluoroalkene C–F Bond Activation
Bibliographic record
Abstract
Herein, a recently reported polyfluoroalkenyl imidazolium salt is shown to react with nitrogen-, oxygen- and sulfur-based nucleophiles at the C β position in a stereoselective and regioselective fashion, without the use of a transition metal. In contrast, reactivity with 1-methylimidazole demonstrates net substitution at C α . This product reacts quantitatively with water, affording clean transformation of a difluoromethylene group to give an α,β-unsaturated trifluoromethyl ketone. Further reactivity studies demonstrate that the difluoromethyl fragment of an N-heterocyclic fluoroalkene is capable of direct C–C bond formation with NaCp through loss of sodium fluoride and double C–F bond activation (Cp = cyclopentadienide). TD-DFT calculations of this product indicate that both the HOMO and LUMO are of mixed π/π* character and are delocalized over the N -heterocyclic and Cp fragments, giving rise to a very intense absorption feature in the UV–vis spectrum. Additionally, two carbonylmetalate-substituted fluorovinyl imidazolium complexes featuring Mn and Mo were isolated and fully characterized.
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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 | 0.000 |
| 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) | 0.001 | 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".