2023/10/06 by Jan M. Rall, Max Lapersonne, Marcel Schorpp +1 · 1 voice · 1 citation
Chemistry · Materials Science · #Organometallic Complex Synthesis and Catalysis #Magnetism in coordination complexes #Synthesis and characterization of novel inorganic/organometallic compounds
paper · pdf · doi:10.1002/anie.202312374
openalex publication_date 2023/10/06 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/02
Abstract We report the synthesis and characterization of the nickelocenium cations [NiCp 2 ]⋅ + and [NiCp 2 ] 2+ as their [F‐Al(OR F ) 3 2 ] − (Cp = C 5 H 5 ; R F =C(CF 3 ) 3 ) salts. Diamagnetic [NiCp 2 ] 2+ represents the first example for the isolation of an unsubstituted parent metallocene dication. Both salts were generated by reacting neutral NiCp 2 with [NO] + [F‐Al(OR F ) 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 1 H NMR of [NiCp 2 ] 2+ is a singlet at 8.6 ppm, whereas paramagnetic [NiCp 2 ]⋅ + is significantly shifted upfield to −103.1 ppm.