Bibliographic record
Abstract
Hydrogen-bridged radical cations (HBRCs) are an intriguing subclass of ion-molecule complexes. They may act as key intermediates of remarkable stability in both association and dissociation reactions of heteroatom-containing molecular ions. The H-bridge of such an HBRC can promote isomerization of its ionic component by H-transfer. Proton-transport catalysis (PTC) is a prime example. Here, a neutral molecule promotes the smooth transformation of an ion into its H-shift isomer by consecutive proton-transfer reactions. A celebrated case is the water catalyzed isomerization of CH(3)OH(•+) into its more stable distonic isomer (•)CH(2)OH(2)(+). Other early studies of PTC also deal with catalyzing 1,2-H shifts in association reactions. This short review focuses on more recent combined experimental and computational studies of catalysis in HBRCs. Mechanisms involving both proton and H atom transfers have been proposed for a variety of systems of H-shift isomers. It has also become clear that PTC is not confined to bimolecular reactions. It also features in the unimolecular chemistry of heteroatom- containing ions, which have a tendency to isomerize to HBRCs en route to their dissociation.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 | 0.001 |
| 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 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".