Synthesis and structures of mono(β-diiminato) copper complexes and their catalytic performances for homo- and copolymerizations of methyl acrylate

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• 作者：Liwei Wang ; Xiangqian You ; Qingliang You ; Tingcheng Li…
• 刊名：Transition Metal Chemistry
• 出版年：2016
• 出版时间：November 2016
• 年：2016
• 卷：41
• 期：8
• 页码：857-866
• 全文大小：1,192 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Catalysis
  Physical Chemistry
  Inorganic Chemistry
  
• 出版者：Springer Netherlands
• ISSN：1572-901X
• 卷排序：41

文摘

A series of mono(β-diiminato) copper complexes bearing different coordinating anions and with different fluorine substitution patterns on the β-diiminato ligands were synthesized. All of the complexes were characterized by physicochemical and spectroscopic methods, and in addition, the structures of two of them were confirmed by X-ray diffraction. The crystal structures revealed a four-coordinate mode around the copper center in a slightly distorted square planar geometry, with the β-diimine and the carboxyl groups coordinated to give six- and four-membered chelate rings. The conjugation of C=C and C=N in the β-diiminato ligands and the resonance between C–O and C=O in the carboxyl groups resulted in extensive delocalization of electrons and the formation of conjugated N–C–C–C–N and O–C–O π-bonds, respectively. When activated by modified methylaluminoxane (MMAO), these complexes can effectively catalyze methacrylate (MA) polymerization with activities up to 54.5 kg/mol Cu h, as well as MA/1-hexene copolymerization with the incorporation of MA over 80 %.