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Zwitterionic Design Principle of Nickel(II) Catalysts for Carbonylative Polymerization of Cyclic Ethers
Yiwei Dai1, Shiyu He1, Bangan Peng1
1Department of Polymer Science, The University of Akron, Akron, OH, 44325-3909, USA.
Abstract:
Zwitterionic structure is necessary for NiII complexes to catalyze carbonylative polymerization (COP) of cyclic ethers. The cationic charge at the NiII center imparts sufficient electrophilicity to the Ni-acyl bond for it to react with cyclic ethers to give an acyl-cyclic ether oxonium intermediate, while the ligand-centered anionic charge ensures that the resultant oxonium cation is ion-paired with the Ni0 nucleophile. The current catalysts give non-alternating copolymers of carbon monoxide and cyclic ethers and are the most effective when both ethylene oxide and tetrahydrofuran are present as the cyclic ether monomers.
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