Department of Chemistry, University of California, Davis, One Shield Avenue, Davis, CA, 95616, USA.
Fukui Institute for Fundamental Chemistry, Kyoto University, Takano Nishi-Hiraki-cho, 34-4, Sakyo-ku, Kyoto, 606-8103, Japan.
Angew Chem Int Ed Engl. 2016 Aug 22;55(35):10444-7. doi: 10.1002/anie.201605061. Epub 2016 Jul 15.
The synthesis of the first linear coordinated Cu(II) complex Cu{N(SiMe3 )Dipp}2 (1 Dipp=C6 H5 -2,6Pr(i) 2 ) and its Cu(I) counterpart Cu{N(SiMe3 )Dipp}2 (2) is described. The formation of 1 proceeds through a dispersion force-driven disproportionation, and is the reaction product of a Cu(I) halide and LiN(SiMe3 )Dipp in a non-donor solvent. The synthesis of 2 is accomplished by preventing the disproportionation into 1 by using the complexing agent 15-crown-5. EPR spectroscopy of 1 provides the first detailed study of a two-coordinate transition-metal complex indicating strong covalency in the Cu-N bonds.
描述了首例线性配位的 Cu(II) 配合物 Cu{N(SiMe3 )Dipp}2（1 Dipp=C6 H5 -2,6Pr(i) 2 ）及其 Cu(I) 对应物 Cu{N(SiMe3 )Dipp}2 （2）的合成。1 的形成是通过色散力驱动的歧化反应进行的，是 Cu(I) 卤化物和 LiN(SiMe3 )Dipp 在非供电子溶剂中的反应产物。2 的合成是通过使用络合剂 15-冠-5 来防止歧化成 1 来完成的。1 的 EPR 光谱提供了首例对两配位过渡金属配合物的详细研究，表明 Cu-N 键具有强烈的共价性。
