一种稳定的镍茂二价阳离子盐的合成与表征
Synthesis and Characterization of a Stable Nickelocenium Dication Salt.
作者信息
Rall Jan M, Lapersonne Max, Schorpp Marcel, Krossing Ingo
机构信息
Institut für Anorganische und Analytische Chemie und Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg, Albertstr. 21, 79104, Freiburg, Germany.
Institut für Anorganische Chemie, Uni Regensburg, Universitätsstraße 31, 93053, Regensburg, Germany.
出版信息
Angew Chem Int Ed Engl. 2023 Nov 20;62(47):e202312374. doi: 10.1002/anie.202312374. Epub 2023 Oct 25.
We report the synthesis and characterization of the nickelocenium cations [NiCp ]⋅ and [NiCp ] as their [F-{Al(OR ) } ] (Cp = C H ; R =C(CF ) ) salts. Diamagnetic [NiCp ] represents the first example for the isolation of an unsubstituted parent metallocene dication. Both salts were generated by reacting neutral NiCp with [NO] [F-{Al(OR ) } ] in 1,2,3,4-tetrafluorobenzene (4FB). The salts were characterized by single crystal X-ray diffraction (XRD), indicating shorter metal-ligand bond lengths for the higher charged salt. Powder XRD shows the salts to be phase pure, cyclic voltammetry in 4FB gave quasi reversible redox waves at -0.44 (0→1) and +1.17 V (1→2) vs Fc/Fc . The H NMR of [NiCp ] is a singlet at 8.6 ppm, whereas paramagnetic [NiCp ]⋅ is significantly shifted upfield to -103.1 ppm.
我们报道了二茂镍阳离子[NiCp₂]⁺和[NiCp₂]²⁺作为其[F₃-{Al(OR₂)₃}]⁻（Cp = C₅H₅；R = C(CF₃)₃）盐的合成与表征。抗磁性的[NiCp₂]²⁺代表了分离出未取代母体茂金属二价阳离子的首个实例。这两种盐都是通过在1,2,3,4 - 四氟苯（4FB）中使中性NiCp₂与[NO]⁺[F₃-{Al(OR₂)₃}]⁻反应生成的。通过单晶X射线衍射（XRD）对这些盐进行了表征，结果表明电荷更高的盐具有更短的金属 - 配体键长。粉末XRD显示这些盐为纯相，在4FB中的循环伏安法在相对于Fc/Fc⁺为 - 0.44（0→1）和 + 1.17 V（1→2）处给出准可逆的氧化还原波。[NiCp₂]²⁺的¹H NMR在8.6 ppm处为单峰，而顺磁性的[NiCp₂]⁺则显著上移至 - 103.1 ppm。
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