The methylene- and ethylene-bridged bis-hydroxylamines HONMe(CH2)nNMeOH (n = 1, 2) were reacted with [Cp*TiCl3], [Cp*ZrCl3] and [Cp*HfCl3] in the presence of MeLi to give the complexes [Cp*TiMe(η2-ONMe)2CH2}] (1), [Cp*TiMe(η2-ONMeCH2)2}] (2), [Cp*ZrMe(η2-ONMeCH2)2}] (3) and [Cp*HfMe(η2-ONMeCH2)2}] (4). The reaction of 2 with AlMe3 afforded the adduct [Cp*TiMeη2-[O(AlMe3)NMe]CH2CH2-η2-(NMeO)}] (2·AlMe3). The compounds were characterised by NMR spectroscopy, elemental analyses and mass spectrometry. Their crystal structures were determined by X-ray diffraction. In each case, all four donor atoms of the [2 + 2]-dentate ligands coordinate in a η2-manner to the organometallic [Cp*MMe] complex fragments. The polymerisation reactions of ethylene and propylene catalysed by 2 activated with methylalumoxane (MAO) were examined.
亚甲基和亚乙基双
羟胺 HONMe(
CH2)nNMeOH(n = 1,2)与[Cp*TiCl3]反应、[Cp*ZrCl3]和[Cp*HfCl3]反应,得到[Cp*TiMe(δ-2-ONMe)2 }] (1)、[Cp*TiMe(δ-2-ONMe )2}] (2)、[Cp*ZrMe(δ-2-ONMe )2}] (3)和[Cp*HfMe(δ-2-ONMe )2}] (4)复合物。2 与 AlMe3 反应生成加合物 [Cp*TiMeÎ-2-[O(AlMe3)NMe] -Î-2-(NMeO)}] (2Â-AlMe3)。这些化合物通过核磁共振光谱、元素分析和质谱法进行了表征。它们的晶体结构是通过 X 射线衍射测定的。在每种情况下,[2 + 2]配位体的所有四个供体原子都以δ-2 方式配位到有机
金属 [Cp*MMe] 复合物片段上。研究了 2 与甲基铝氧烷 (MAO) 活化催化的
乙烯和
丙烯聚合反应。