Syntheses of Heterometallic Neodymium−Zinc Complexes and Their Performance in the Copolymerization of CO2 and Cyclohexene Oxide
Quanyou Yao1, Yaorong Wang1, Bei Zhao1, Xuehua Zhu3, Yunjie Luo2,*（罗云杰）, Dan Yuan1,*（袁丹）, and Yingming Yao1,*（姚英明）
1 Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Dushu Lake Campus, Soochow University, Suzhou 215123, People’s Republic of China
2 School of Materials Science and Chemical Engineering, Key Laboratory of Advanced Mass Spectrometry and Molecular Analysis of Zhejiang Province, Ningbo University, Ningbo 315211, People’s Republic of China
3 School of Chemistry and Life Science, Suzhou University of Science and Technology, Suzhou 215009, People’s Republic of China
Inorg. Chem. 2022, 61, 10373--10382
A series of Nd–Zn heterometallic complexes bearing o-phenylenediamine-bridged tris(phenolato) ligands (L) were synthesized and characterized. By tuning the backbones of ancillary tris(phenolato) ligands and initiating benzyloxy groups, a Nd–Zn heterometallic complex 12 (ClLNdZnOBnCF3) was found to be highly active for the copolymerization of CO2 and cyclohexene oxide (CHO) to produce perfect alternating poly(cyclohexene carbonate) with a high turnover frequency up to 5640 h–1 under the polymerization of 90 °C and 20 bar CO2 pressure. The kinetics study showed that CO2/CHO copolymerization catalyzed by 12 was the first order dependence of 12 and CHO concentration and the zero-order dependence of CO2 pressure. The reaction of 12 with CO2 generated a carbonate-coordinated [NdZnNd] trinuclear complex 13, which was believed to be the key intermediate to initiate CO2/CHO copolymerization. On the basis of some experiments, a plausible synergistic polymerization mechanism was proposed.
链接：//pubs.acs.org/doi/10.1021/acs.inorgchem.2c00920
