Influence of the number of water molecules on the mechanism of <i>N</i>-sulfinylaniline hydrolysis
Bibliographic record
Abstract
The mechanism of the uncatalyzed hydrolysis of N-sulfinylaniline (Ph-N=S=O) has been studied with B3LYP/6-31+G(2d,2p) in the gas phase, with explicit treatment of water molecules. Hydrolysis involves water attack on sulfur, with a close to perpendicular alignment of a water molecule and the NSO plane in both prereaction complexes and transition states for the rate-determining step. Consequently, the distance of the weak S···O interaction, together with the efficiency of protonation of either nitrogen (attack across the N=S bond) or oxygen (attack across the S=O bond) atoms of the NSO group, determines the height of the activation barrier for hydrolysis. While the reaction with one water molecule is characterized by an unreasonably high enthalpy of activation, a cooperative effect from the weak interactions appears with the inclusion of a second water molecule, where both participate in the reaction, and the activation enthalpy drops significantly. The preference for attack across the S=O bond that is found in the reaction with one water molecule switches to a dominance of attack across the N=S bond in the reaction with three water molecules.Key words: N-sulfinylaniline, hydrolysis, mechanism, density functional theory (DFT).
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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 | 0.000 | 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 | 0.001 | 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 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".