Chasing the Mond Cation: Synthesis and Characterization of the Homoleptic Nickel Tetracarbonyl Cation and its Tricarbonyl‐Nitrosyl Analogue

130 years after Mond discovered the first homoleptic carbonyl complex Ni(CO)4, we report on a [Ni(CO)4].+ salt as synthesis of any nickel cation in condensed phase. It was prepared by oxidation metal with synergistic oxidant Ag[F{Al(ORF)3}2]/0.5 I2 (RF=C(CF3)3) CO atmosphere. This D2d-symmetric metalloradical represents last missing entry among structurally characterized cations Groups 6 to 11. Additionally, tricarbonyl-nitrosyl [Ni(CO)3(NO)]+ obtained usage NO[F{Al(ORF)3}2] and all products were fully means IR, Raman, NMR/EPR, single crystal powder XRD.