Cobalt Complexes Supported by cis-Macrocyclic Diphosphines: Synthesis, Reactivity, and Activity toward Coupling Carbon Dioxide and Ethylene
| Autor: | Ioana Knopf, Christopher C. Cummins, Marc-André Courtemanche |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
chemistry.chemical_classification
Acrylate Ethylene 010405 organic chemistry Dimer Organic Chemistry chemistry.chemical_element 010402 general chemistry 01 natural sciences 0104 chemical sciences Catalysis Coordination complex Inorganic Chemistry chemistry.chemical_compound chemistry Diphosphines Polymer chemistry Reactivity (chemistry) Physical and Theoretical Chemistry Cobalt |
| Zdroj: | Organometallics. 36:4834-4843 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/acs.organomet.7b00734 |
| Popis: | 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 Cy2–DPC (1), was primarily used as a model diphosphine. Cobalt(II) dihalide diphosphine complexes such as (Cy2–DPC)CoX2, 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, [(Cy2–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(PPh3)3 was also found to be active in mediating acrylate production. As pa... |
| Databáze: | OpenAIRE |
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