Zirconium Complexes of Fluorinated Aryl Diamides
详细信息 查看全文
- 作者：Paul E. O'Connor ; Darryl J. Morrison ; Sheryl Steeves ; Katherine Burrage ; and David J. Berg
- 刊名：Organometallics
- 出版年：2001
- 出版时间：March 19, 2001
- 年：2001
- 卷：20
- 期：6
- 页码：1153 - 1160
- 全文大小：136K
- 年卷期：v.20,no.6(March 19, 2001)
- ISSN：1520-6041
文摘
The reaction of excess ArFNHLi with (ICH2CH2OCH2)2 affords the new diamines (ArFNHCH2CH2OCH2)2 (1, ArF = C6F5; 2, ArF = 3,5-C6H3(CF3)2) in moderate yield. Direct protonolysisof Zr(CH2Ph)nCl4-n (n = 2-4) or Zr[N(SiMe3)2]nCl4-n (n = 2, 3) with 1 or 2 (1 equiv) affordsthe zirconium complexes Zr(ArFNCH2CH2OCH2)2(X)(Y) (ArF = C6F5: 3, X = Y = Cl; 4, X =N(SiMe3)2, Y = Cl; 5, X = Cl, Y = CH2Ph; 6, X = Y = CH2Ph. ArF = 3,5-C6H3(CF3)2: 7, X =Y = Cl; 8, X = Y = CH2Ph). The structures of 1, 4, 5, and 7 were established by X-raycrystallography with the zirconium complexes 4, 5, and 7 all adopting a monocapped trigonalbipyramidal geometry in the solid state. However, in solution, these complexes display highersymmetry due to rapid ligand rearrangement. The silylamido complex 4 shows restrictedrotation of the C6F5 rings in solution (
G
= 49 ± 3 kJ mol-1). Abstraction of a benzyl groupfrom 6 by B(C6F5)3 affords {Zr[CH2OCH2CH2N(C6F5)]2(CH2Ph)}+{(PhCH2)B(C6F5)3}- (9). Thiscomplex shows evidence for 
2-benzyl coordination and does not polymerize ethylene at roomtemperature. Treatment of 3 with excess MAO (500 equiv) and ethylene (1 atm, 50 
C) affordspolyethylene at a modest rate (3.2 kg mol-1 Zr h-1).
G = 49 ± 3 kJ mol-1). Abstraction of a benzyl groupfrom 6 by B(C6F5)3 affords {Zr[CH2OCH2CH2N(C6F5)]2(CH2Ph)}+{(PhCH2)B(C6F5)3}- (9). Thiscomplex shows evidence for 2-benzyl coordination and does not polymerize ethylene at roomtemperature. Treatment of 3 with excess MAO (500 equiv) and ethylene (1 atm, 50 C) affordspolyethylene at a modest rate (3.2 kg mol-1 Zr h-1).