Theoretical Study of the Intrinsic Reactivities of Various Allylmetals toward Carbonyls and Water
Bibliographic record
Abstract
Quantum mechanics MP2/6-31+G* calculations have been carried out for the reactions of a series of monomeric allylmetals with water and carbonyl compounds in the gas phase. Allyl complexes of groups IA and IIA and low-valent group IIIA and IVA metals are π-complexes or reactive σ-complexes. They show high reactivities toward hydrolysis. Group IIB, trivalent group IIIA, tetravalent group IVA, and both tri- and pentavalent group VA metals form σ-complexes with allyl. These allylmetals are less reactive toward hydrolysis than toward allylation. The calculated intrinsic kinetic preference of allylation over hydrolysis is found to correlate well with the reactivity of hydrolysis, the nucleophilicity of the allylmetals, and the lateness of hydrolysis transition structures. Both the nucleophilicity of the allylmetal complexes and the thermodynamic driving force are important to the reactivity of hydrolysis. Importantly, there is a large thermodynamic preference for allylation over hydrolysis for all allylmetals because the hydrolysis has to break a strong O−H bond. Thus, the kinetic preference for allylation is correlated with the degree of H−O bond breaking in the hydrolysis transition structure.
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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 | 0.001 | 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 | 0.000 |
| Research integrity | 0.001 | 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".