Theoretical Calculations on the Tetramethyldisilene Rearrangement: A New Approach to an Old Mechanistic Problem
Bibliographic record
Abstract
Roark and Peddle first observed that, when not trapped, Me(2)Si=SiMe(2) underwent a series of rearrangements to give two major isomeric products: 1,1-dimethyl-1,3-disilacyclobutane and 1,3-dimethyl-1,3-disilacyclobutane. The widely accepted mechanism for this rearrangement was proposed by Barton and co-workers. However, little is known about the thermodynamic or kinetic properties of this reaction, because the relevant data are limited to the product ratios of the two isomers. Our calculations predict that the product ratio is driven by kinetic control rather than thermodynamic control. We also show that new DFT functionals, such as MPW1K and M052X, produce thermochemical results comparable with CCSD(T) calculations.
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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 | 0.001 |
| 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 | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.005 | 0.001 |
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".