(eta(3)-Azaallyl)zirconium Chlorides: Synthesis, Characterization, and Ethylene (Co-)polymerization Activity

doi:10.1021/om100133b

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	(eta(3)-Azaallyl)zirconium Chlorides: Synthesis, Characterization, and Ethylene (Co-)polymerization Activity
	Yuan, Shifang 1,2,3; Bai, Shengdi 1; Liu, Diansheng 1; Sun, Wen-Hua2,3
刊名	ORGANOMETALLICS
	2010-05-10
卷号	29 期号:9 页码:2132-2138
ISSN号	0276-7333
DOI	10.1021/om100133b
英文摘要	(2,6-Diisopropyl-N-(1-phenylvinyl)benzenamido)magnesium bromide (CH2(Ph)C(2,6-(Pr2C6H3)-Pr-i)-NMgBr center dot 2THF, 1b) reacted with 1 equiv of Me2NMe2SiCl to form the N-(2-((dimethylamino)dimethylsilyl)-1-phenylvinyl)-2,6-diisopropylbenzenamine (1c). The stoichiometric reaction of 1c with lithium diisopropylamide (LDA) formed lithium N-(2-((dimethylamino)dimethylsilyl)-1-phenyl-vinyl)-2,6-diisopropylbenzenamidate (Me2NMe2SiCH(Ph)C(2,6-(Pr2C6H3)-Pr-i)NLi center dot 3THF, 1d) in high yields. The reaction of zirconium tetrachloride with 2 equiv of id produced the bisligated (eta(3)-azaallyl)zirconium dichloride ((eta(3)-(2,6-(Pr2C6H3)-Pr-i)N(Ph)CCHSiMe2NMe2)(2)ZrCl2, 2), whereas the stoichiometric reaction of zirconium tetrachloride with 1d formed a monoligated zirconium trichloride complex ((eta(3):eta(1)-(2,6-(Pr2C6H3)-Pr-i)N(Ph)CCHSiMe2NMe2)ZrCl3, 3), in which the ligand acted as an eta(3)-azaallyl species with N-donation via the dimethylamino group at the silyl bridge. All compounds were fully characterized by elemental and spectroscopic analyses and metal compounds by single-crystal X-ray diffraction. The azaallyl groups of the ligands act in a kappa(1)-enamido fashion in compounds 1b,d, while the azaallyls appear as an eta(3)-N,C,C mode in compound 2. The eta(3):eta(1) coordination of the azaallyl and dimethylsilyl groups provided a sterically constrained geometry around the zirconium in compound 3. The coordination geometries around each zirconium are pseudo-octahedral in both compounds 2 and 3. The modes of coordination affected their catalytic behaviors toward polymerization: high activity by 3 and good activity by 2.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000277212300020
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/69643]
专题	中国科学院化学研究所
通讯作者	Liu, Diansheng
作者单位	1.Shanxi Univ, Inst Appl Chem, Taiyuan 030006, Peoples R China 2.Chinese Acad Sci, Key Lab Engn Plast, Beijing 100190, Peoples R China 3.Chinese Acad Sci, Beijing Natl Lab Mol Sci, Inst Chem, Beijing 100190, Peoples R China
推荐引用方式 GB/T 7714	Yuan, Shifang,Bai, Shengdi,Liu, Diansheng,et al. (eta(3)-Azaallyl)zirconium Chlorides: Synthesis, Characterization, and Ethylene (Co-)polymerization Activity[J]. ORGANOMETALLICS,2010,29(9):2132-2138.
APA	Yuan, Shifang,Bai, Shengdi,Liu, Diansheng,&Sun, Wen-Hua.(2010).(eta(3)-Azaallyl)zirconium Chlorides: Synthesis, Characterization, and Ethylene (Co-)polymerization Activity.ORGANOMETALLICS,29(9),2132-2138.
MLA	Yuan, Shifang,et al."(eta(3)-Azaallyl)zirconium Chlorides: Synthesis, Characterization, and Ethylene (Co-)polymerization Activity".ORGANOMETALLICS 29.9(2010):2132-2138.