The prospects of cation transfer to chalcogen nucleophiles
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Bibliographic record
Abstract
In this study, we used computational quantum chemistry to investigate the cation affinity for a range of nucleophiles to gauge the possibility of using organochalcogens as catalysts for cation transfer (reference data and geometries are provided in the repository https://github.com/armanderch/ca176 ). In general, the calculated gas-phase cation affinities decrease in the order Cl + > Br + > I + > carbon-centered cation, the anionic nucleophiles have significantly larger cation affinities than the neutral ones, sulfides have larger cation affinities than selenides, and solvation lowers the cation affinities and especially for anionic nucleophiles. These observations are consistent with general chemical intuitions. The energies for the resulting condensed-phase cation transfer reactions show that transferring a carbon-centered cation from a neutral source (e.g., Me 2 CO 3 ) to a chalcogen nucleophile (e.g., Me 2 S) is thermochemically viable. However, they are associated with large kinetic barriers. Overall, we find that SeMeC 6 H 5 may be a suitable catalyst for transferring a carbon-centered cation from an active source such as MeCO 3 R or MeSO 4 R. In this study, we also find that double-hybrid DFT methods, e.g., DSD-PBEP86 to be reasonable for the study of these cation transfer processes.
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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 | 0.000 |
| 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) | 0.002 | 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 it