[1,5] Sigmatropic rearrangements in silolides and germolides—a computational investigation
Bibliographic record
Abstract
[1,5] Sigmatropic rearrangements of different groups R in anionic sila- and germacyclopentadienes (silolides and germolides) were studied by density functional methods. This investigation was prompted by our recent finding that silylene-substituted 1 H-silolides and 1 H-germolides rearrange to the corresponding 2 H-isomers (Chem. Commun. 2024, 60, 11295). The anionic 2 H-silolides and germolides feature a negatively charged E=C double bond (E = Si, Ge) that is integrated in a cyclopentadienyl system. The aim of this computational study is to enable the use of the full synthetic capacity of these novel compounds by identifying optimal substitution patterns at the siloles and germoles that allow their synthesis. The results of our computational study suggest that electron-withdrawing substituents (either by π-resonance or by negative hyperconjugation) at the carbon atom of the E=C double bond significantly favours the 2 H-tetrolides over the 1 H-isomer. In addition, the computations revealed that migrating electropositive groups R such as silyl, boryl, or silylenyl have small calculated barriers for the [1,5] sigmatropic rearrangement (Δ G ‡ < 50 kJ mol −1 ), which allow the 1 H tetrolide → 2 H tetrolide isomerisation to occur at ambient conditions.
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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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 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".