Synthesis of Heterocyclic-Fused Cyclopentadienyl Scandium Complexes and the Catalysis for Copolymerization of Ethylene and Dicyclopentadiene

doi:10.1021/om500992v

CORC > 化学研究所 > 中国科学院化学研究所

	Synthesis of Heterocyclic-Fused Cyclopentadienyl Scandium Complexes and the Catalysis for Copolymerization of Ethylene and Dicyclopentadiene
	Chen, Runhai 1,2; Yao, Changguang 1,4; Wang, Meiyan 3; Xie, Hongyan 1,4; Wu, Chunji 1; Cui, Dongmei 1
刊名	ORGANOMETALLICS
	2015-01-26
卷号	34 期号:2 页码:455-461
ISSN号	0276-7333
DOI	10.1021/om500992v
英文摘要	Heterocyclic-fused cyclopentadienyl scandium bis(alkyl) complexes L1-4Sc(CH2SiMe3)(2)THF ((5-Me-1-Ph-cyclopenta[b]pyrrol-4-yl)Sc(CH2SiMe3)(2)THF (1), (2,5-Me-2-3-Ph-6H-cyclopenta[b]thiophenyl)Sc(CH2SiMe3)(2)THF (2), (2,4,5,6-Me-4-4H-cyclopenta[b]thiophenyl)Sc(CH2SiMe3)(2)THF (3), (2,3,4,5,6-Me-5-4H-cyclopenta[b]thiophenyl)Sc(CH2SiMe3)(2)THF) (4)) were facilely synthesized by alkane elimination reaction of Sc(CH2SiMe3)3(THF)2 with the heterocyclic-fused cyclopentadienyl ligands HL1-4 in high yields. Complexes 1-4 were characterized by H-1 and C-13 NMR spectroscopies and X-ray diffraction analyses as THF-solvated monomers, adopting a half-sandwich geometry. Upon activation of [Ph3C][B(C6F5)(4)]/AliBu(3), these half-sandwich scandium complexes displayed various activities toward the copolymerization of ethylene (E) and dicyclopentadiene (DCPD). Complex 1, supported by the phenyl-substituted pyrrole-fused cyclopentadienyl ligand, showed a slightly higher activity than the phenyl-substituted thiophene-fused cyclopentadienyl complex 2. Among the thiophene-fused cyclopentadienyl complexes 2-4, 4, bearing pentamethyl substituents, showed the highest activity of 2.9 x 10 (6) g/molSc.h.bar. The resultant copolymers had adjustable DCPD incorporation varying from 14.0 up to 46.1 mol %, of which the alternating poly(E-alt-DCPD) had a high Tg of 166 degrees C. In addition, no cross-linking was observed in the copolymers, suggesting that these catalytic systems were highly regioselective for the two active double bonds within DCPD.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000348619700008
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/53459]
专题	中国科学院化学研究所
通讯作者	Wu, Chunji
作者单位	1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Shandong Univ Technol, Sch Chem Engn, Zibo 255049, Peoples R China 3.Jilin Univ, Inst Theoret Chem, State Key Lab Theoret & Computat Chem, Changchun 130022, Peoples R China 4.Univ Chinese Acad Sci, Changchun Branch, Changchun 130022, Peoples R China
推荐引用方式 GB/T 7714	Chen, Runhai,Yao, Changguang,Wang, Meiyan,et al. Synthesis of Heterocyclic-Fused Cyclopentadienyl Scandium Complexes and the Catalysis for Copolymerization of Ethylene and Dicyclopentadiene[J]. ORGANOMETALLICS,2015,34(2):455-461.
APA	Chen, Runhai,Yao, Changguang,Wang, Meiyan,Xie, Hongyan,Wu, Chunji,&Cui, Dongmei.(2015).Synthesis of Heterocyclic-Fused Cyclopentadienyl Scandium Complexes and the Catalysis for Copolymerization of Ethylene and Dicyclopentadiene.ORGANOMETALLICS,34(2),455-461.
MLA	Chen, Runhai,et al."Synthesis of Heterocyclic-Fused Cyclopentadienyl Scandium Complexes and the Catalysis for Copolymerization of Ethylene and Dicyclopentadiene".ORGANOMETALLICS 34.2(2015):455-461.