Activation of Enamido Zirconium Complexes for Ethylene Polymerization: Electrophilic Addition versus Electrophilic Abstraction Reaction
作者:Young Heui Kim、Tae Ho Kim、Na Young Kim、Eun Sook Cho、Bun Yeoul Lee、Dong Mok Shin、Young Keun Chung
DOI:10.1021/om020949p
日期:2003.3.1
6-(CHMe2)2-C6H3}MLMe (L = Cp*, M = Zr, 7; L = Cp*, M = Hf, 8; L = Cp, M = Zr, 9) in 63%, 69% and 90% yields, respectively. The solid-state structure of 7 was determined. When 2, 7, or 9 is treated with 1 equiv of B(C6F5)3, one observes formation of the picolyl- or methyl-abstracted ion-paired complex in NMR spectra. When Al(C6F5)3 is added to 2, 8, or 9, the aluminum atom is coordinated by the methylene functionality
α-二亚胺化合物2,6-(CHMe 2)2 -C 6 H 3 } N C(CH 3)C(CH 3)N 2,6-(CHMe 2)2 -C 6 H 3的去质子化}在THF中有过量的KH,以75%的收率得到二钾N,N '-(1,2-二亚甲基-1,2-乙二基)双(2,6-二异丙基苯胺)(1)。的反应1与双(2-吡啶甲基)二氯化锆通过的ZrCl的反应原位产生的4和2当量的(2-吡啶甲基)钾,得到[ Ñ,Ñ' - (1,2-二亚甲基-1,2-乙二基)双(2,6-二异丙基苯胺基)-κ 2 Ñ,Ñ ']双(2-吡啶甲基)锆(IV)(2)在35%的产率。1与LMCl 3(L = Cp,Cp *; M = Zr,Hf)的相似反应得到所需的络合物2,6-(CHMe 2)2 -C 6 H 3 } NC (CH 2)C (CH 2)N 2,6-(CHMe 2)2 -C 6 H 3 } MLCl(L = Cp