Highly efficient ethylene/norbornene copolymerization by o-Di(phenyl)phosphanylphenolate-based half-titanocene complexes

doi:10.1002/pola.26528

CORC > 化学研究所 > 中国科学院化学研究所

	Highly efficient ethylene/norbornene copolymerization by o-Di(phenyl)phosphanylphenolate-based half-titanocene complexes
	Tang, Xiao-Yan 1,2; Wang, Yong-Xia 1; Li, Bai-Xiang 1; Liu, Jing-Yu 1; Li, Yue-Sheng 1
刊名	JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
	2013-04-01
卷号	51 期号:7 页码:1585-1594
关键词	Calculations Catalysts Copolymerization
ISSN号	0887-624X
DOI	10.1002/pola.26528
英文摘要	A series of o-di(phenyl)phosphanylphenolate-based half-titanocene complexes CpTiCl2[O-2-R1-4-R2-6-(Ph2P)C6H2] (Cp = C5H5, 2a: R1 = R2 = H; 2b: R1 = F, R2 = H; 2c: R1 = Ph, R2 = H; 2d: R1 = SiMe3, R2 = H; 2e: R1 = tBu, R2 = H; 2f: R1 = R2 = tBu) have been synthesized in high yields (6587%) by treating CpTiCl3 with 1.0 equiv of the deprotonated ligands in THF. The 1H and 31P NMR spectra indicated that the phosphorus is not coordinated to titanium in complexes 2ac, but is coordinated to titanium in complexes 2df. Structures for 2cf were further confirmed by X-ray crystallography. Complex 2c is essentially a four-coordinate tetrahedral geometry, whereas complexes 2d-f adopt five-coordinate distorted squarepyramid geometry around the titanium center. All complexes exhibited low to moderate activities toward homopolymerization of ethylene. Excitingly, they displayed excellent ability to copolymerize ethylene with norbornene, and catalytic activity was more than 100 times larger than that of ethylene homopolymerization in the case of Ph3CB(C6F5)4/iBu3Al as cocatalyst, affording the copolymers with high comonomer incorporations. Moreover, DFT calculations study had been performed to shed light on the active species and the fundamental role of NBE in improving the catalytic activity. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 1585-1594
语种	英语
出版者	WILEY-BLACKWELL
WOS记录号	WOS:000315495100011
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/47047]
专题	中国科学院化学研究所
通讯作者	Liu, Jing-Yu
作者单位	1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Chinese Acad Sci, Grad Sch, Changchun Branch, Changchun 130022, Peoples R China
推荐引用方式 GB/T 7714	Tang, Xiao-Yan,Wang, Yong-Xia,Li, Bai-Xiang,et al. Highly efficient ethylene/norbornene copolymerization by o-Di(phenyl)phosphanylphenolate-based half-titanocene complexes[J]. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY,2013,51(7):1585-1594.
APA	Tang, Xiao-Yan,Wang, Yong-Xia,Li, Bai-Xiang,Liu, Jing-Yu,&Li, Yue-Sheng.(2013).Highly efficient ethylene/norbornene copolymerization by o-Di(phenyl)phosphanylphenolate-based half-titanocene complexes.JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY,51(7),1585-1594.
MLA	Tang, Xiao-Yan,et al."Highly efficient ethylene/norbornene copolymerization by o-Di(phenyl)phosphanylphenolate-based half-titanocene complexes".JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 51.7(2013):1585-1594.