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Chasing the Mond Cation: Synthesis and Characterization of the Homoleptic Nickel Tetracarbonyl Cation and its Tricarbonyl‐Nitrosyl Analogue
Author(s) -
Schmitt Manuel,
Mayländer Maximilian,
Goost Julian,
Richert Sabine,
Krossing Ingo
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202102216
Subject(s) - homoleptic , nickel , chemistry , electron paramagnetic resonance , raman spectroscopy , metal , inorganic chemistry , salt (chemistry) , crystallography , organic chemistry , nuclear magnetic resonance , physics , optics
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.