Activation of Molecular Hydrogen and Oxygen by PSiP Complexes of Cobalt
Bibliographic record
Abstract
The syntheses of Co II halide complexes supported by κ 3 ‐(2‐Cy 2 PC 6 H 4 ) 2 SiMe (Cy‐PSiP) ligation are detailed. Reduction of (Cy‐PSiP)Co(PMe 3 )I could be achieved under mild conditions using magnesium metal to generate the Co I complex (Cy‐PSiP)Co(PMe 3 )N 2 in high yield. When this reaction was carried out under an atmosphere of CO, (Cy‐PSiP)Co(CO) 2 was obtained. Unlike the facile reduction of Co II to Co I , attempts to access Co III species supported by Cy‐PSiP ligation proved challenging. Attempted oxidative addition reactions involving (Cy‐PSiP)Co(PMe 3 )N 2 were generally unsuccessful, with the sole exception of H 2 , which reacted to afford the dihydride complex (Cy‐PSiP)Co(PMe 3 )(H) 2 . The dihydride complex undergoes Co‐H site exchange in solution and readily eliminates H 2 . The Co I precursor (Cy‐PSiP)Co(PMe 3 )N 2 is a competent precatalyst for the hydrogenation of terminal alkenes. Exposure of (Cy‐PSiP)CoI to O 2 gas under anhydrous conditions led to rapid ligand oxidation at Si and P, with no evidence observed at low temperature for a Co III superoxo or peroxo intermediate. Exclusive oxidation at Si to afford a Co II ‐siloxy complex was observed upon treatment of (Cy‐PSiP)CoI with one equiv. Me 3 NO. While this siloxy complex did not react further with O 2 , treatment with a second equiv. of Me 3 NO led to subsequent oxidation involving one phosphino donor. This observation supports the notion that in the ligand oxidation reactivity observed with O 2 , the O atoms incorporated at both Si and P are likely derived from the same O 2 molecule.
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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".