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 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 | 0.000 |
| 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 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".