Zwitterionic Design Principle of Nickel(II) Catalysts for Carbonylative Polymerization of Cyclic Ethers. (2nd October 2018)

• Record Type: Journal Article
• Authors: Dai, Yiwei; He, Shiyu; Peng, Bangan; Crandall, Laura A.; Schrage, Briana R.; Ziegler, Christopher J.; Jia, Li
• Is Part Of: Angewandte Chemie. Volume 130:Number 43(2018)
• Page Start: 14307
• Page End: 14311
• Publication Date: 2018-10-02
• Subjects: Carbonylierung -- Katalyse -- Kohlenmonoxid -- Polymerisation -- Zwitterionen; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201808507
• Languages: English
• ISSNs: 0044-8249

Abstract

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 Ni 0 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.