Synthesis of amine-bridged bis(phenolate) rare-earth metal aryloxides and their catalytic performances for the ring-opening polymerization of L-lactic acid O-carboxyanhydride and L-lactide

doi:10.1039/c7dt03001k

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	Synthesis of amine-bridged bis(phenolate) rare-earth metal aryloxides and their catalytic performances for the ring-opening polymerization of L-lactic acid O-carboxyanhydride and L-lactide
	Ouyang, Hao 1,2; Nie, Kun 1,2,3; Yuan, Dan 1,2; Yao, Yingming 1,2,4
刊名	DALTON TRANSACTIONS
	2017-12-07
卷号	46 期号:45 页码:15928-15938
ISSN号	1477-9226
DOI	10.1039/c7dt03001k
英文摘要	A series of rare-earth metal complexes stabilized by different amine bridged bis(phenolate) ligands were synthesized and well characterized. Their catalytic performances for the ring-opening polymerization of L-lactic acid O-carboxyanhydride (L-lacOCA) and L-lactide were explored. Sequential reactions of amine bridged bis(phenol) with (C5H5)(3)RE(THF) in a 1 : 1 molar ratio, followed by 1 equivalent of p-cresol gave the amine bridged bis(phenolate) rare-earth metal aryloxides {La[NNOO-R](OC6H4-4CH(3))(THF)}(2) {[NNOO-R] = Me2NCH2CH2N}{CH2-(2-O-C6H2-R-2-3,5)}(2), R = Me (1), La[NNOO-R] (OC6H4-4-CH3)(THF)(2) [R = Bu-t (2); R = Cumyl (3)], Y[NNOO-R](OC6H4-4-CH3)(THF) [R = Bu-t (4)] and {Y[THFONOO-Bu-t](OC6H4-4-CH3)}(2) {THFONOO-Bu-t = (CH2)(3)OCHCH2N[CH2-(2-O-C6H2-3,5-Bu-t(2))](2)} (5) in good isolated yields. Single-crystal structure determination revealed that complexes 1 and 5 have dimeric structures, whereas complexes 2 and 3 have monomeric structures in the solid state. It was found that these complexes are efficient initiators for the ring-opening polymerization of L-lacOCA, and the overall coordination environments around the metal centers and the ionic radii of the metal centers have an obvious influence on the catalytic performance. A comparative study on the polymerization kinetics of L-lacOCA and L-lactide initiated by complex 5 was carried out for the first time. The results obtained demonstrated that the polymerization of L-lacOCA and L-lactide is first order for the catalyst and monomer concentration in dichloromethane, respectively, and the Gibbs energy of activation of L-lacOCA and L-lactide is found to be essentially the same. Mechanistic studies revealed that L-lacOCA polymerization initiated by these rare-earth metal complexes proceeded via a coordination-insertion mechanism.
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000415989000037
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/45065]
专题	中国科学院化学研究所
通讯作者	Nie, Kun; Yao, Yingming
作者单位	1.Soochow Univ, Suzhou Key Lab Macromol Design & Precis Synth, Key Lab Organ Synth Jiangsu Prov, Coll Chem Chem Engn & Mat Sci, Dushu Lake Campus, Suzhou 215123, Peoples R China 2.Soochow Univ, State & Local Joint Engn Lab Novel Funct Polymer, Coll Chem Chem Engn & Mat Sci, Dushu Lake Campus, Suzhou 215123, Peoples R China 3.Taishan Univ, Sch Chem & Chem Engn, Tai An 271021, Shandong, Peoples R China 4.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Jilin, Peoples R China
推荐引用方式 GB/T 7714	Ouyang, Hao,Nie, Kun,Yuan, Dan,et al. Synthesis of amine-bridged bis(phenolate) rare-earth metal aryloxides and their catalytic performances for the ring-opening polymerization of L-lactic acid O-carboxyanhydride and L-lactide[J]. DALTON TRANSACTIONS,2017,46(45):15928-15938.
APA	Ouyang, Hao,Nie, Kun,Yuan, Dan,&Yao, Yingming.(2017).Synthesis of amine-bridged bis(phenolate) rare-earth metal aryloxides and their catalytic performances for the ring-opening polymerization of L-lactic acid O-carboxyanhydride and L-lactide.DALTON TRANSACTIONS,46(45),15928-15938.
MLA	Ouyang, Hao,et al."Synthesis of amine-bridged bis(phenolate) rare-earth metal aryloxides and their catalytic performances for the ring-opening polymerization of L-lactic acid O-carboxyanhydride and L-lactide".DALTON TRANSACTIONS 46.45(2017):15928-15938.