Barium complexes with crown-ether-functionalised amidinate and iminoanilide ligands for the hydrophosphination of vinylarenes
作者:Erwann Le Coz、Hanieh Roueindeji、Thierry Roisnel、Vincent Dorcet、Jean-François Carpentier、Yann Sarazin
DOI:10.1039/c9dt01512d
日期:——
The detailed multistep syntheses of two nitrogen-based sterically congested iminoanilidine and amidine proligands bearing a tethered 15-member aza-ether-crown macrocycle, namely I^Acrown}H and Amcrown}H, are reported. These proligands react with [BaN(SiMe2H)2}2·(thf)n] to generate the heteroleptic barium complexes [I^Acrown}BaN(SiMe2H)2] (5) and [Amcrown}BaN(SiMe2H)2] (6) in high yields. These
据报道,带有氮系的15元氮杂-醚-冠状大环,即I ^ A冠} H和Am冠} H的两个基于氮的空间拥挤的亚氨基丙啶和and pro配体的详细的多步合成方法。这些配体与[Ba N(SiMe 2 H)2 } 2 ·(thf)n ]反应生成杂合钡络合物[I ^ A Crown } BaN(SiMe 2 H)2 ](5)和[Am冠} BaN(SiMe 2 H)2 ](6)高产。这些配合物表现出很高的配位数(分别为8和7),并通过轻度的Ba⋯H-Si相互作用而稳定。异常地为亲氧性元件,诸如钡,在脒基配体6仅η 1配位的。配合物5和6介导苯乙烯与伯(PhPH 2)和仲(HPPh 2)膦的分子间加氢磷酸化。在这些反应中,它们的催化性能优于其他钡预催化剂。在5催化的HPPh 2催化的苯乙烯氢磷酸化过程中,磷络合物[I ^ A Crown } BaPPh2 ]( 7)可被截取并进行晶体学表征。