Cobalt Complexes Supported by <i>cis</i>-Macrocyclic Diphosphines: Synthesis, Reactivity, and Activity toward Coupling Carbon Dioxide and Ethylene
Bibliographic record
Abstract
The coordination chemistry of cis -macrocyclic diphosphines readily accessed from white phosphorus was explored, with a focus on preparing and studying cobalt complexes. cis -1,6-Dicyclohexyl-3,4,8,9-tetramethyl-2,5,7,10-tetrahydro-1,6-DiPhospheCine, or Cy 2 –DPC ( 1 ), was primarily used as a model diphosphine. Cobalt(II) dihalide diphosphine complexes such as (Cy 2 –DPC)CoX 2, X = Cl ( 2 ) and I ( 3 ), were prepared, and their reactivity toward a variety of reducing agents was studied. We were successful in preparing and structurally characterizing an unusual iodide-bridged cobalt(I) dimer, [(Cy 2 –DPC)CoI] 2 ( 8 ). These cobalt complexes were also investigated as potential catalysts for the coupling of carbon dioxide and ethylene to produce acrylate, a valuable polymer precursor. Although not yet catalytic, the first examples of cobalt complexes capable of mediating this transformation are reported. Notably, the well-known commercial complex ClCo(PPh 3 ) 3 was also found to be active in mediating acrylate production. As part of our mechanistic investigation, a pseudotetrahedral cobalt methyl acrylate complex, (Cy 2 –DPC)CoI(CH 2 CHCOOMe) ( 10 ), was prepared and structurally characterized.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 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) | 0.000 | 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".