Chasing the Mond Cation: Synthesis and Characterization of the Homoleptic Nickel Tetracarbonyl Cation and its Tricarbonyl‐Nitrosyl Analogue
Manuel Schmitt, Maximilian Mayländer, Julian Goost, Sabine Richert, Ingo Krossing
Abstract
Abstract 130 years after Mond discovered the first homoleptic carbonyl complex Ni(CO) 4 , we report on a [Ni(CO) 4 ] .+ salt as the first synthesis of any homoleptic nickel carbonyl cation in the condensed phase. It was prepared by oxidation of nickel metal with the synergistic oxidant Ag[F{Al(OR F ) 3 } 2 ]/0.5 I 2 (R F =C(CF 3 ) 3 ) in CO atmosphere. This D 2d ‐symmetric metalloradical represents the last missing entry among the structurally characterized homoleptic carbonyl cations of Groups 6 to 11. Additionally, the nickel tricarbonyl‐nitrosyl cation [Ni(CO) 3 (NO)] + was obtained by usage of NO[F{Al(OR F ) 3 } 2 ] and all products were fully characterized by means of IR, Raman, NMR/EPR, single crystal and powder XRD.