From Inert to Explosive, The Hydrolytic Reactivity of R−NSO Compounds Understood: A Computational Study
Bibliographic record
Abstract
We present a computational study on the concerted hydrolysis of several classes of N-sulfinylamines of generic formula R-N═S═O, such as the -amines themselves (R-NSO), -hydrazines (R-NH-NSO), -hydrazides (R-CO-NH-NSO) and -amides (R-CO-NSO), as these species are known to possess a wide range of hydrolytic reactivity. Two possible mechanisms of hydrolysis, with a water dimer across the S═O and N═S bonds, in the gas phase are investigated. The reactivity is discussed with respect to the electronic structures, established with the use of the quantum theory of Atoms in Molecules, Natural Bond Orbital and Natural Resonance Theory approaches. For the inert N-sulfinylhydrazines and the keto tautomers of N-sulfinylhydrazides, extended π-conjugation adds a sulfide-like resonance structure that is responsible for their insensitivity toward moisture. Activation barriers for hydrolysis, where water acts as a nucleophilic reagent, decrease with increasing positive charge on the NSO sulfur atom, a finding that might prove useful as a predictive tool in the determination of the general reactivity of an N-sulfinyl compound by experimentalists.
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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 | 0.002 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.002 | 0.001 |
| Insufficient payload (model declined to judge) | 0.004 | 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".