Zwitterionic Design Principle of Nickel(II) Catalysts for Carbonylative Polymerization of Cyclic Ethers

Yiwei Dai; Shiyu He; Bangan Peng; Laura A. Crandall; Briana R. Schrage; Christopher J. Ziegler; Li Jia

doi:10.1002/anie.201808507

Zwitterionic Design Principle of Nickel(II) Catalysts for Carbonylative Polymerization of Cyclic Ethers

Yiwei Dai, Shiyu He, Bangan Peng, Laura A. Crandall, Briana R. Schrage, Christopher J. Ziegler, Li Jia

Research output: Contribution to journal › Article › peer-review

16 Scopus citations

Abstract

Zwitterionic structure is necessary for Ni^II complexes to catalyze carbonylative polymerization (COP) of cyclic ethers. The cationic charge at the Ni^II 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.

Original language	English
Pages (from-to)	14111-14115
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	43
DOIs	https://doi.org/10.1002/anie.201808507
State	Published - Oct 22 2018
Externally published	Yes

Funding

The research is supported by the National Science Foundation (CHE-1266442). C.J.Z. acknowledges The University of Akron for support of this research. L.J. thanks Dr. Eite Drent for helpful discussions and suggestions. We thank Dr. Jessi A. Baughman for his assistance with the diffusion NMR experiments.

Funders	Funder number
National Science Foundation	CHE-1266442
University of Akron

Keywords

carbon monoxide
carbonylation
catalysis
polymerization
zwitterions

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10.1002/anie.201808507

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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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AU - Dai, Yiwei

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AU - Crandall, Laura A.

AU - Schrage, Briana R.

AU - Ziegler, Christopher J.

AU - Jia, Li

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AB - 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.

KW - carbon monoxide

KW - carbonylation

KW - catalysis

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Zwitterionic Design Principle of Nickel(II) Catalysts for Carbonylative Polymerization of Cyclic Ethers

Abstract

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