A series of o-phenylenediamine bridged tris(phenolate)ligand-stabilized rare-earth metal complexes were synthesized and characterized.Lanthanum(complex 1),neodymium(complex 2^(tBu)),and yttrium(complex 3)complexes sta...A series of o-phenylenediamine bridged tris(phenolate)ligand-stabilized rare-earth metal complexes were synthesized and characterized.Lanthanum(complex 1),neodymium(complex 2^(tBu)),and yttrium(complex 3)complexes stabilized by ligand of buiky tert-butyl substituents are mononuclear,whereas neodymium complexes 2^(Me)and 2^(C1)bearing smaller methyl and chloro substituents are dinuclear,respectively.They were applied in the alternating copolymerization of CO_(2)and cyclohexene oxide.The addition of benzyl alcohol is beneficial to improving yields(up to 86%)and selectivity of poly(carbonate)(up to 99%).Stoichiometric reaction of benzyl alcohol with rare-earth metal complexes 1 and 2^(tBu)results in formation of complexes 4 and 5 as dinuclear complexes with benzyl alcohol coordination,which was confirmed via single crystal X-ray diffraction analysis,and nuclear magnetic resonance(NMR)spectroscopy(for 4).Complex 5 shows equally good activity and selectivity of that of complex 2^(tBu)and benzyl alcohol,consolidating that complex 5 is indeed generated during polymerization.The neodymium tris(phenolate)5 is one of the few examples of rare-earth metal complex as a single-component initiator for copolymerization of epoxide and CO_(2).Matrix-assisted laser desorption ionization-time of flight(MALDI-TOF)mass spectrometry analysis proves benzyloxy group as the chain end.^(1)H NMR monitoring suggests that the insertion of CO_(2)may be the first step in the growth of the polymer chain.展开更多
基金Project supported by the National Natural Science Foundation of China(21871198)the Major Research Project of the Natural Science of the Jiangsu Higher Education Institutions(19KJA360005)the Open Research Fund of State Key Laboratory of Rare-Earth Resource Utilization(CIAC)and PAPD。
文摘A series of o-phenylenediamine bridged tris(phenolate)ligand-stabilized rare-earth metal complexes were synthesized and characterized.Lanthanum(complex 1),neodymium(complex 2^(tBu)),and yttrium(complex 3)complexes stabilized by ligand of buiky tert-butyl substituents are mononuclear,whereas neodymium complexes 2^(Me)and 2^(C1)bearing smaller methyl and chloro substituents are dinuclear,respectively.They were applied in the alternating copolymerization of CO_(2)and cyclohexene oxide.The addition of benzyl alcohol is beneficial to improving yields(up to 86%)and selectivity of poly(carbonate)(up to 99%).Stoichiometric reaction of benzyl alcohol with rare-earth metal complexes 1 and 2^(tBu)results in formation of complexes 4 and 5 as dinuclear complexes with benzyl alcohol coordination,which was confirmed via single crystal X-ray diffraction analysis,and nuclear magnetic resonance(NMR)spectroscopy(for 4).Complex 5 shows equally good activity and selectivity of that of complex 2^(tBu)and benzyl alcohol,consolidating that complex 5 is indeed generated during polymerization.The neodymium tris(phenolate)5 is one of the few examples of rare-earth metal complex as a single-component initiator for copolymerization of epoxide and CO_(2).Matrix-assisted laser desorption ionization-time of flight(MALDI-TOF)mass spectrometry analysis proves benzyloxy group as the chain end.^(1)H NMR monitoring suggests that the insertion of CO_(2)may be the first step in the growth of the polymer chain.