Alkyl Effects on the Chain Initiation Efficiency of Olefin Polymerization by Cationic Half-Sandwich Scandium Catalysts: A DFT Study

doi:10.1021/acs.organomet.6b00081

	Alkyl Effects on the Chain Initiation Efficiency of Olefin Polymerization by Cationic Half-Sandwich Scandium Catalysts: A DFT Study
	Kang, Xiaohui 1,2; Zhou, Guangli 1; Wang, Xingbao 1; Qu, Jingping 1; Hou, Zhaomin 1,3,4; Luo, Yi 1
刊名	ORGANOMETALLICS
	2016-03-28
卷号	35 期号:6 页码:913-920
ISSN号	0276-7333
DOI	10.1021/acs.organomet.6b00081
文献子类	Article
英文摘要	The effect of alkyls on the chain initiation efficiency of :ethylene, propene, 1-hexene, styrene, butadiene, and isoprene polymerizations catalyzed by the half-sandwich cationic rare-earth-metal alkyl complexes [(eta(5)-C5Me5)ScR](+) (R = CH2SiMe3, 1; R = o-CH2C6H4NMe2, 2; R = eta(3)-C3H5, 3) has been studied by using a DFT approach. It has been found that 2 with the largest sterically demanding aminobenzyl group results in the lowest initiation efficiency and thus longest induction period among the three catalysts investigated. In contrast, 1 with CH2SiMe3 displays the best chain initiation ability, and 3 with eta(3)-allyl gives moderate chain initiation activity, mainly due to the most stable resulting coordination complex. Species 1 and 3 have better regioselectivity in the chain initiation of styrene polymerization than species 2. In addition, species 1' ([eta(5)-C5Me5)Sc(CH2SiMe3)THF](+)) with a THF ligand has better chain initiation efficiency in styrene and isoprene polymerizations than species 2 but is reasonably worse than the analogue 1 without a THF ligand.
WOS关键词	AB-INITIO PSEUDOPOTENTIALS ; ZIEGLER-NATTA CATALYSIS ; ETHYLENE POLYMERIZATION ; PROPENE POLYMERIZATION ; STYRENE-ETHYLENE ; METAL-CATALYSTS ; COPOLYMERIZATION ; COMPLEXES ; MECHANISM ; PROPAGATION
WOS研究方向	Chemistry
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000373247300010
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/170674]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Hou, Zhaomin; Luo, Yi
作者单位	1.Dalian Univ Technol, Sch Pharmaceut Sci & Technol, State Key Lab Fine Chem, Dalian 116024, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, Natl Chromatog R&A Ctr, CAS Key Lab Separat Sci Analyt Chem, Dalian 116023, Peoples R China 3.RIKEN, Organometall Chem Lab, 2-1 Hirosawa, Wako, Saitama 3510198, Japan 4.RIKEN, Ctr Sustainable Resource Sci, 2-1 Hirosawa, Wako, Saitama 3510198, Japan
推荐引用方式 GB/T 7714	Kang, Xiaohui,Zhou, Guangli,Wang, Xingbao,et al. Alkyl Effects on the Chain Initiation Efficiency of Olefin Polymerization by Cationic Half-Sandwich Scandium Catalysts: A DFT Study[J]. ORGANOMETALLICS,2016,35(6):913-920.
APA	Kang, Xiaohui,Zhou, Guangli,Wang, Xingbao,Qu, Jingping,Hou, Zhaomin,&Luo, Yi.(2016).Alkyl Effects on the Chain Initiation Efficiency of Olefin Polymerization by Cationic Half-Sandwich Scandium Catalysts: A DFT Study.ORGANOMETALLICS,35(6),913-920.
MLA	Kang, Xiaohui,et al."Alkyl Effects on the Chain Initiation Efficiency of Olefin Polymerization by Cationic Half-Sandwich Scandium Catalysts: A DFT Study".ORGANOMETALLICS 35.6(2016):913-920.