Hydroboration of Carbon Dioxide Using Ambiphilic Phosphine–Borane Catalysts: On the Role of the Formaldehyde Adduct
Why this work is in the frame
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Bibliographic record
Abstract
Ambiphilic phosphine–borane derivatives 1-B(OR) 2 -2-PR′ 2 –C 6 H 4 (R′ = Ph ( 1 ), i Pr ( 2 ); (OR) 2 = (OMe) 2 ( 1a, 2a ); catechol ( 1b, 2b ) pinacol ( 1c, 2c ), −OCH 2 C(CH 3 ) 2 CH 2 O– ( 1d )) were tested as catalysts for the hydroboration of CO 2 using HBcat or BH 3 ·SMe 2 to generate methoxyboranes. It was shown that the most active species were the catechol derivatives 1b and 2b . In the presence of HBcat, without CO 2, ambiphilic species 1a, 1c, and 1d were shown to transform to 1b, whereas 2a and 2c were shown to transform to 2b . The formaldehyde adducts 1b·CH 2 O and 2b·CH 2 O are postulated to be the active catalysts in the reduction of CO 2 rather than being simple resting states. Isotope labeling experiments and density functional theory (DFT) studies show that once the formaldehyde adduct is generated, the CH 2 O moiety remains on the ambiphilic system through catalysis. Species 2b·CH 2 O was shown to exhibit turnover frequencies for the CO 2 reduction using BH 3 ·SMe 2 up to 228 h –1 at ambient temperature and up to 873 h –1 at 70 °C, mirroring the catalytic activity of 1b .
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.002 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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 it