Synthesis and Characterization of a Stable Nickelocenium Dication Salt |
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| Authors: | Jan M. Rall Max Lapersonne Prof. Dr. Marcel Schorpp Prof. Dr. Ingo Krossing |
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| Affiliation: | 1. Institut für Anorganische und Analytische Chemie und Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg, Albertstr. 21, 79104 Freiburg, Germany;2. Institut für Anorganische Chemie, Uni Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany |
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| Abstract: | We report the synthesis and characterization of the nickelocenium cations [NiCp2]⋅+ and [NiCp2]2+ as their [F-{Al(ORF)3}2]− (Cp = C5H5; RF=C(CF3)3) salts. Diamagnetic [NiCp2]2+ represents the first example for the isolation of an unsubstituted parent metallocene dication. Both salts were generated by reacting neutral NiCp2 with [NO]+[F-{Al(ORF)3}2]− 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 1H NMR of [NiCp2]2+ is a singlet at 8.6 ppm, whereas paramagnetic [NiCp2]⋅+ is significantly shifted upfield to −103.1 ppm. |
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| Keywords: | Cyclovoltammetry Dication Metallocene Nickel Weakly Coordinating Anion |
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