Calculated Hydride and Fluoride Affinities of a Series of Carbenium and Silylium Cations in the Gas Phase and in C<sub>6</sub>H<sub>5</sub>Cl Solution
Bibliographic record
Abstract
We report the hydride and fluoride affinities for a group of silylium and carbenium cations. With comparable substituents on the central atom, the silylium cations have the higher fluoride affinity, whereas the carbenium ions have the higher hydride affinity. In the first approximation, the hydride and the fluoride affinities vary in parallel with changes in substitution, but the deviations from linear correspondence of hydride and fluoride affinities are more pronounced for carbenium ions. The hydride and fluoride affinities of silylium cations are very similar, whereas for carbenium ions, the hydride affinities are 35-60 kcal mol(-1) higher than fluoride affinities. These results are placed in the context of studies of hydrodefluorination of aliphatic C-F bonds enabled by silylium carborane catalysts [C. Douvris, O. V. Ozerov, Science 2008, 321, 1188]. The abstraction of fluoride from perfluoroalkanes by a trialkylsilylium cation is neither thermodynamically favorable nor kinetically accessible and, if at all possible, will require a much more fluorophilic silylium cation.
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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 | 0.001 | 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 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.002 |
| 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".