Selective Ni-Catalyzed Hydroboration of CO<sub>2</sub> to the Formaldehyde Level Enabled by New PSiP Ligation
Bibliographic record
Abstract
The synthesis and characterization of group 10 metal pincer complexes supported by a new bis(indolylphosphino)silyl ligand are described, including the synthesis of Ni, Pd, and Pt hydride species. Solution NMR and single-crystal X-ray data revealed that a significant amount of structural variability is possible for such hydride complexes, particularly in the case of Ni, where terminal Ni- H as well as complexes involving η 2 -SiH coordination are both accessible and may even coexist, in ratios dependent on factors such as the nature of additional coligands, including N 2 from the reaction atmosphere, as well as solvent and temperature. Nickel and palladium hydride complexes of this new ligand were found to exhibit divergent selectivity in the catalytic hydroboration of CO 2 with pinacolborane (HBPin). While the Pd catalyst exhibited moderate activity for CO 2 hydroboration to the formate level, the analogous Ni species exhibited unprecedented selectivity (97%) for hydroboration of CO 2 to the formaldehyde level to provide the bis(boryl)acetal PinBOCH 2 OBPin in high yield, under mild conditions. The HBPin-derived bis(boryl)acetal can be successfully isolated and utilized as a source of methylene for the formation of C–N and C–P bonds.
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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 | 0.000 | 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 | 0.001 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 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".