Synthesis and characterization of novel chromium complexes based on beta-enaminoketonato ligands and their application to ethylene polymerization

doi:10.1016/j.molcata.2014.07.006

CORC > 化学研究所 > 中国科学院化学研究所

	Synthesis and characterization of novel chromium complexes based on beta-enaminoketonato ligands and their application to ethylene polymerization
	Liu, Jing-Yu; Tao, Ping; Li, Yue-Sheng
刊名	JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
	2014-11-15
卷号	394 页码:162-169
关键词	Ziegler-natta Polymerization Catalysts Polyolefin
ISSN号	1381-1169
DOI	10.1016/j.molcata.2014.07.006
英文摘要	A series of novel non-Cp-based chromium(III) complexes bearing tridentate beta-enaminoketonato chelating ligands of type, [(RNC)-N-2(CF3)C(H)(CRO)-O-1]CrCl2(thf) (2a: R-1 = Bu-t, R-2 = -C6H4OMe(o); 2b: R-1 = Bu-t, R-2 = -C9H6N; 2c: R-1 = Bu-t, R-2 = -C6H4SMe(o); 2d: R-1 =Ph, R-2 = -C9H6N; 2e: R-1 = Ph, R-2 = -C6H4SMe(o)) have been prepared in high yields (e.g. 63-79%) from CrCl3(thf)(3) by treating with 1.0 equiv. of the deprotonated ligands in tetrahydrofuran. These complexes were identified by IR, and mass spectra as well as elemental analysis. Structures for 2b, 2c and 2e were further confirmed by X-ray crystallography. Non-Cp-based chromium(III) complexes have six-coordinate distorted octahedral geometry, and the heteroatom in the sidearm is coordinated to chromium. When activated by modified methylaluminoxane, complexes 2b and 2c exhibited high activities towards ethylene polymerization. These results indicated that both the donor atoms in side arm and the substituents in backbone significantly affected polymerization behaviors. In order to further explore the structure-reactivity relationship of the catalysts, we synthesized some novel half-sandwich chromium(III) complexes, Cp[(RNC)-N-2(CF3)C(H)(CRO)-O-1]CrCl (3a: R-1 = Bu-t, R-2 = -C6H4OMe(o); 3c: R-1 = Bu-t, R-2 = -C6H4SMe(o); 3e: R-1 = Ph, R-2 = -C6H4SMe(o)) and investigated their potential application in ethylene polymerization under the similar conditions. Complex 3c adopts a three-legged piano stool geometry with a pseudo-octahedral coordination environment, and the heteroatom in the sidearm is not coordinated to chromium. These half-sandwich chromium complexes all displayed high activities for ethylene polymerization under the same conditions. Neither the donor atom in side arm nor the substituent in backbone significantly affected polymerization behaviors, in complete contrast to the results by non-Cp-based chromium catalysts. (C) 2014 Elsevier B.V. All rights reserved.
语种	英语
出版者	ELSEVIER SCIENCE BV
WOS记录号	WOS:000342185300020
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/50693]
专题	中国科学院化学研究所
通讯作者	Li, Yue-Sheng
作者单位	Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China
推荐引用方式 GB/T 7714	Liu, Jing-Yu,Tao, Ping,Li, Yue-Sheng. Synthesis and characterization of novel chromium complexes based on beta-enaminoketonato ligands and their application to ethylene polymerization[J]. JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL,2014,394:162-169.
APA	Liu, Jing-Yu,Tao, Ping,&Li, Yue-Sheng.(2014).Synthesis and characterization of novel chromium complexes based on beta-enaminoketonato ligands and their application to ethylene polymerization.JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL,394,162-169.
MLA	Liu, Jing-Yu,et al."Synthesis and characterization of novel chromium complexes based on beta-enaminoketonato ligands and their application to ethylene polymerization".JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 394(2014):162-169.