The reactivity of diarylmethyl carbocations within non-protic zeolites
Bibliographic record
Abstract
The generation of diarylmethyl carbocations within non-protic zeolites (LiY, NaY, KY, RbY, CsY, and NaX) was carried out via laser excitation (266 nm or 266 nm / 308 nm) of diarylacetic acids. Rapid loss of CO2, followed by photochemical oxidation of the diarylmethyl radicals resulted in the formation of the diarylmethyl carbocations. The reactivity of the diarylmethyl carbocations was found to be highly dependent on the alkali metal counterion and the Si/Al ratio of the zeolite framework. Furthermore, the effect of various para-electron donating substituents (4-H, 3-CH3, 4-CH3, 4,4′-CH3, and 4-OCH3) on the diarylmethyl carbocation reactivity was investigated. Comparison of the Hammett plots constructed for the reactivity of the diarylmethyl carbocations in zeolites with those in solution (CH3CN–H2O (1:2) and TFE) showed decreased sensitivity of the electrophilic species towards para-electron donating substituents in the heterogeneous media. The leveling effect observed in the zeolite Hammett plots has been attributed to the presence of an isokinetic relationship, specifically, a low isokinetic temperature for the reaction of diarylmethyl carbocations with the aluminosilicate zeolite framework.
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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) | 0.000 | 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 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".