(9). Complexes 2, 3, 5, and 8 were characterized by X-ray crystallography. Complexes 5 and 6 were observed to undergo protonolysis with various acids (HA) to give mixed [Zr]MeA complexes. Reaction of complex 6 with isonitriles (ArNC) gave the η2-iminoacyl complex (Cp)(Trop)ZrMe[N(Ar)CMe] (13), whose structure was confirmed by X-ray crystallography. All the complexes displayed dynamic behavior, and
合成了一类新的带有托
吡啶基(Trop)
配体的4族配合物。这种新颖的阴离子
配体很容易衍生自
天然产物Tropine,被认为是经过深入研究的Cp
配体的类似物(Cp =
环戊二烯基),并具有双环系统,其中烯丙基官能团提供4π电子,胺官能团提供2σ电子到达
金属中心。第4族配合物的合成涉及用第4族
金属卤化物对甲
锡烷基化的烯丙基官能度进行
金属转移,同时消除Me 3 SnCl。内甲
锡烷基化的托帕定(1)与ZrCl 4,CpZrCl 3或CpTiCl 3反应,得到配合物(Trop)2 ZrCl 2(2),(Cp)(Trop)ZrCl 2(3)和(Cp)(Trop)TiCl 2(4)。使用
甲基锂将这些二卤化物络合物烷基化以生成(Trop)2 ZrMe 2(5),(Cp)(Trop)ZrMe 2(6),(Cp)(Trop)TiMe 2(7)或
苄基氯化镁以生成(Trop) )2 ZrBn 2(8)和(Cp)(Trop)ZrBn