Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors

doi:10.1021/ja711146t

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	Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors
	Gao, Wei 1,2; Cui, Dongmei 1
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2008-04-09
卷号	130 期号:14 页码:4984-4991
ISSN号	0002-7863
DOI	10.1021/ja711146t
英文摘要	The first aryldiimine NCN-pincer ligated rare earth metal dichlorides (2,6-(2,6-C(6)H(3)R(2)N=CH)(2)C(6)H(3))LnCl(2)(THF)(2) (Ln = Y, R = Me (1), Et (2), Pr (3); R = Et, Ln = La (4), Nd (5), Gd (6), Sm (7), Eu (8), Tb (9), Dy (10), Ho (11), Yb (12), Lu (13)) were successfully synthesized via transmetalation between 2,6-(2,6-C(2)H(3)-R(2)N=CH)(2)-C(6)H(3)Li and LnCl(3)(THF)(1 similar to 3.5). These complexes are isostructural monomers with two coordinating THF molecules, where the pincer ligand coordinates to the central metal ion in a kappa C:kappa N: kappa N' tridentate mode, adopting a meridional geometry. Complexes 1-6, 9-11, and 13 combined with aluminum tris(alkyl)s and [Ph(3)C][B(C(6)F(5))(4)] established a homogeneous Ziegler-Natta catalyst system, which exhibited high activities and excellent cis-1,4 selectivities for the polymerizations of butadiene (T(p) = 25 degrees C, 99.9%; 0 degrees C, 100%) and isoprene (T(p) = 25 degrees C, 98.8%). Remarkably, such high cis-1,4 selectivity almost remained at elevated polymerization temperatures up to 80 degrees C and did not vary with the type of the central lanthanide element, however, which was influenced obviously by the ortho substituent of the N-aryl ring of the ligands and the bulkiness of the aluminum alkyls. The Ln-Al bimetallic cations were considered as the active species. These results shed new light on improving the catalytic performance of the conventional Ziegler-Natta catalysts for the specific selective polymerization of dienes.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000254643900054
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/63471]
专题	中国科学院化学研究所
通讯作者	Cui, Dongmei
作者单位	1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Jilin Univ, Sch Chem, Changchun 130012, Peoples R China
推荐引用方式 GB/T 7714	Gao, Wei,Cui, Dongmei. Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2008,130(14):4984-4991.
APA	Gao, Wei,&Cui, Dongmei.(2008).Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,130(14),4984-4991.
MLA	Gao, Wei,et al."Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 130.14(2008):4984-4991.