Journal
MACROMOLECULES
Volume 43, Issue 5, Pages 2291-2298Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma902582m
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Funding
- EPSRC [EP/C544846/1, EP/C544838/1]
- Engineering and Physical Sciences Research Council [EP/C544838/1, EP/C544846/1] Funding Source: researchfish
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The synthesis and characterization of three new cobalt catalysts for the copolymerization of carbon dioxide and cyclohexene oxide are reported. All the complexes are extremely active at just 1 atm pressure of carbon dioxide, with very high selectivity for copolymerization and carbonate formation. The catalysts are dicobalt(II/II and II/III) and tricobalt(II/II/II) complexes coordinated by a macrocyclic, reduced Robson type ancillary ligand and by acetate groups. The complexes are significantly more active than their direct zinc analogues, which we attribute to the increased nucleophilicity of the cobalt-oxygen bond in the cobalt-carbonate propagating species. All three complexes are characterized using mass spectrometry, infrared and ultraviolet-visible spectroscopies, elemental analysis, and, for the tricobalt complex and mixed valence dicobalt species, single-crystal X-ray crystallography.
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