Nickel and Palladium Complexes of Pyridine−Phosphine Ligands as Ethene Oligomerization Catalysts
作者:Jitte Flapper、Huub Kooijman、Martin Lutz、Anthony L. Spek、Piet W. N. M. van Leeuwen、Cornelis J. Elsevier、Paul C. J. Kamer
DOI:10.1021/om800903n
日期:2009.2.23
Pyridine−phosphine ligands 1−5 have been used to prepare neutral nickel dichloride complexes, neutral methylpalladium chloride complexes, and cationic methylpalladium complexes. The ligands consist of a diphenylphosphine and a pyridine moiety and differ in the backbone connecting those donor groups. Nickel complexes 9−13 are paramagnetic complexes, and they were characterized by elemental analysis, high-resolution
吡啶膦配体1 - 5已被用来制备中性二氯化镍配合物,中性methylpalladium氯配合物,和阳离子methylpalladium络合物。配体由二苯基膦和吡啶部分组成,并且在连接那些供体基团的主链上不同。镍配合物9 - 13是顺磁性配合物,并对其进行了表征通过元素分析,高分辨率质谱,而且,对于10和12,单晶X射线衍射。中性钯配合14 - 18进行了充分的特点。对络合物15进行单晶X射线衍射和16,以及可变温度NMR证明16显示出金属环的缓慢转化。阳离子钯物种19 - 23从氯化物抽象后的中性配合物获得。像其中性前体一样,21显示出缓慢的环反转。用MAO活化后,将镍物质评估为乙烯低聚催化剂。所有配合物均具有高活性,TOF在24×10 3和85×10 3之间(mol C 2 H 4)·(mol Ni·h)-1。在所有情况下,丁烯都是主要产物,占产物的76至96 mol%。1-丁烯的选择性