Asymmetric Copolymerization of CO2 with meso-Epoxides Mediated by Dinuclear Cobalt(III) Complexes: Unprecedented Enantioselectivity and Activity†
Ye Liu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (P. R. China)
Search for more papers by this authorWei-Min Ren
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (P. R. China)
Search for more papers by this authorJie Liu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (P. R. China)
Search for more papers by this authorCorresponding Author
Prof. Dr. Xiao-Bing Lu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (P. R. China)
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (P. R. China)Search for more papers by this authorYe Liu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (P. R. China)
Search for more papers by this authorWei-Min Ren
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (P. R. China)
Search for more papers by this authorJie Liu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (P. R. China)
Search for more papers by this authorCorresponding Author
Prof. Dr. Xiao-Bing Lu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (P. R. China)
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (P. R. China)Search for more papers by this authorGratitude is expressed to the National Natural Science Foundation of China (NSFC, Grant 21134002, 21104007), and National Basic Research Program of China (973 Program: 2009CB825300). X.-B. Lu gratefully acknowledges the Chang Jiang Scholars Program (T2011056) from the Ministry of Education of the People’s Republic of China. We are also grateful to Prof. Cheng He and Dr. Haiyan An for their kind assistance in X-ray crystallographic analysis.
Graphical Abstract
Isotaktisch: In der asymmetrischen Copolymerisation von CO2 mit meso-Epoxiden (darunter das wenig reaktive Cyclopentenoxid), die von dem zweikernigen CoIII-Komplex (S,S,S,S)-1 unter milden Bedingungen katalysiert wurde, wurde beispiellose Enantioselektivität und katalytische Aktivität beobachtet. Die Copolymere enthalten mehr als 99 % Carbonateinheiten und sind perfekt isotaktisch.
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Molecular structure of dinuclear SalenAlIIICl (hydrogen atoms and uncoordinated solvent omitted for clarity; carbon atoms are unlabeled). Thermal ellipsoids are at the 30 % probability level. The complex displays an Al–Al distance of 7.89 Å and an exo phenyl–phenyl dihedral angle of 45.1°.
- 18Notably, the use of other nucleophilic cocatalysts, such as simple nBu4NCl, could significantly improve the activity of the dinuclear CoIII catalyst. However, the copolymerization is very sensitive to water, so the avoidance of water or the decrease to a great extent in the reaction system is necessary for obtaining a high reaction rate and copolymers with highly molecular weight.
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