Lone Pair−π and π−π Interactions Play an Important Role in Proton-Coupled Electron Transfer Reactions
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Bibliographic record
Abstract
Proton-coupled electron transfer (PCET), a class of formal hydrogen atom transfer (HAT) reactions, is of widespread interest because it is implicated in a broad range of chemical and biochemical processes. PCET is typically differentiated from HAT by the fact that it occurs when a proton and electron are transferred between different sets of molecular orbitals. Previous theoretical work predicted that hydrogen bonding between reactants is a necessary but not sufficient condition for H exchanges to take place by PCET. This implies that HAT is the only mechanism for H exchange between two carbon atoms. In this work, we present computational results that show that the H exchange in the tert-butylperoxyl/phenol couple, a prototypical antioxidant exchange reaction, occurs by PCET and that the transfer of the electron can occur via an oxygen lone pair-ring pi overlap. We then show that the H exchange in a model for the tyrosyl/tyrosine couple, which is implicated in ribonucleotide reductase chemistry, occurs via PCET and that one path for the electron transfer is provided by a strong pi-stacking interaction. Finally, we show that a pi-stacking interaction in the benzyl/toluene couple, a system in which there is no H-bonding, can result in this exchange occurring via PCET to some extent. Collectively, these results indicate that PCET reactions are not unique to systems that can engage in H-bonding and that lone pair-pi and pi-pi interactions in these systems may be more important than previously understood.
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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 | 0.001 | 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 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
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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