The role of H<sub>2</sub>O in the electron transfer-activation of substrates using SmI<sub>2</sub>: insights from DFT
Bibliographic record
Abstract
The first detailed theoretical study on the synthetically important electron transfer (ET) reductant SmI2-H2O has been conducted in the context of the activation of important alkyliodide, ketone, lactone and ester substrates, processes of importance in cross-coupling. Our studies give major insights into the nature of the reagent and suggest that; (i) H2O has a high affinity for Sm(ii) and displaces iodine from the metal center; (ii) SmI2-H2O has 6-7 molecules of H2O directly bound to the metal center; (iii) binding of H2O to Sm(II) promotes coordination of the substrate to Sm(II) and subsequent ET; (iv) resultant ketyl radicals are stabilized by hydrogen-bonding to H2O. The findings add greatly to the understanding of SmI2-H2O and the role of H2O in ET processes, and will facilitate the design of new processes initiated by reductive ET.
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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 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 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".