Synthesis and Characterization of Amine-Bridged Bis(phenolate) Yttrium Guanidinates and Their Application in the Ring-Opening Polymerization of 1,4-Dioxan-2-one

doi:10.1021/om5008242

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	Synthesis and Characterization of Amine-Bridged Bis(phenolate) Yttrium Guanidinates and Their Application in the Ring-Opening Polymerization of 1,4-Dioxan-2-one
	Zeng, Tinghua 1,2; Wang, Yaorong 1,2; Shen, Qi 1,2; Yao, Yingming 1,2,3; Luo, Yunjie 4; Cui, Dongmei 3
刊名	ORGANOMETALLICS
	2014-12-08
卷号	33 期号:23 页码:6803-6811
ISSN号	0276-7333
DOI	10.1021/om5008242
英文摘要	A series of neutral yttrium guanidinates supported by an amine-bridged bis(phenolate) ligand were synthesized, and their catalytic behaviors for the ring-opening polymerization of 1,4-dioxan-2-one (p-dioxanone, PDO) were explored. Metathesis reactions of amine-bridged bis(phenolate) yttrium chlorides LLnCl(THF) [L = Me2NCH2CH2N{CH2-(2-OC6H2-tBu(2)-3,5)}2] with corresponding lithium guanidinates generated in situ in a 1:1 molar ratio in THF gave the neutral yttrium guanidinates LY[R2NC(NR1)(2)] [R-1 = -Cy, R2N = -N(TMS)(2) (1), -NiPr2 (2), -N(CH2)(5) (3); R-1 = -iPr, R2N = -NiPr2 (4) -NPh2 (5))]. These complexes were well characterized by elemental analyses, IR, and NMR spectroscopy. The definitive molecular structures of these complexes were determined by single-crystal X-ray analysis. It was found that these complexes can efficiently initiate the ring-opening polymerization (ROP) of PDO, and the catalytic activity is affected by the nature of the guanidinate groups with the active sequence of 1 > 2 approximate to 3 approximate to 4 > 5. The influences of reaction conditions such as polymerization time, polymerization temperature, and molar ratio of monomer to initiator on the polymerization were also investigated. The polymerization kinetics of PDO catalyzed by complex 1 is first-order with respect to monomer concentration, and the apparent activation energy amounts to 30.8 kJ mol(-1). The mechanistic investigations showed that the ROP of PDO proceeded through a coordinationinsertion mechanism with a rupture of the acyloxygen bond of the monomer. MALDI-TOF mass spectrum analysis of the oligomer revealed that there are two kinds of polymer chains in this catalytic system, e.g., the linear chains H[OCH2CH2OCH2CO](n)OH and the PPDO macrocycles.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000346114900013
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/50131]
专题	中国科学院化学研究所
通讯作者	Wang, Yaorong
作者单位	1.Soochow Univ, Coll Chem Chem Engn & Mat Sci, Key Lab Organ Synth Jiangsu Prov, Suzhou 215123, Peoples R China 2.Soochow Univ, Coll Chem Chem Engn & Mat Sci, Suzhou Key Lab Macromol Design & Precis Synth, Suzhou 215123, Peoples R China 3.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 4.Zhejiang Univ, Ningbo Inst Technol, Organometall Chem Lab, Ningbo 315100, Zhejiang, Peoples R China
推荐引用方式 GB/T 7714	Zeng, Tinghua,Wang, Yaorong,Shen, Qi,et al. Synthesis and Characterization of Amine-Bridged Bis(phenolate) Yttrium Guanidinates and Their Application in the Ring-Opening Polymerization of 1,4-Dioxan-2-one[J]. ORGANOMETALLICS,2014,33(23):6803-6811.
APA	Zeng, Tinghua,Wang, Yaorong,Shen, Qi,Yao, Yingming,Luo, Yunjie,&Cui, Dongmei.(2014).Synthesis and Characterization of Amine-Bridged Bis(phenolate) Yttrium Guanidinates and Their Application in the Ring-Opening Polymerization of 1,4-Dioxan-2-one.ORGANOMETALLICS,33(23),6803-6811.
MLA	Zeng, Tinghua,et al."Synthesis and Characterization of Amine-Bridged Bis(phenolate) Yttrium Guanidinates and Their Application in the Ring-Opening Polymerization of 1,4-Dioxan-2-one".ORGANOMETALLICS 33.23(2014):6803-6811.