Effects of Hyperconjugation on the Electronic Structure and Photoreactivity of Organic Sulfonyl Chlorides
Bibliographic record
Abstract
The electronic structure of organic sulfonyl compounds of the form RSO(2)G (G = -Cl, -OH, -CH(3)) is investigated to evaluate the effect of aryl R groups on photocleavage of the S-G bond. Sulfur K-edge X-ray absorption spectroscopy (XAS) provides a direct measure of the empty low-lying molecular orbitals in these complexes and, in combination with DFT calculations, a detailed description of the bonding in these compounds. The presence of an aryl group bound to the sulfonyl moiety has a significant impact on the spectroscopy and electronic structure of the site. The analysis suggests that the SCl(sigma*) orbital is significantly affected by mixing with the aryl pi* manifold. This mixing is dependent upon the nature of G and is most pronounced in the sulfonyl chlorides, where the energy of the SCl(sigma*) orbital is lowered by approximately 0.5 eV. The observed mixing is best described as excited-state hyperconjugation of the aryl pi system into the SCl(sigma*) orbital. The magnitude of the effect can be estimated directly from the S K-edge XAS spectra. These results are discussed in relation to the observed photochemistry of RSO(2)Cl, which is significantly enhanced when R = aryl as compared to alkyl substituents.
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 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) | 0.002 | 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 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".