Isolation and Characterization of the Homoleptic Nickel(I) and Nickel(II) Bis‐benzene Sandwich Cations

• Published in: Angewandte Chemie International Edition Vol. 61; no. 50; pp. e202211555 - n/a
• Main Authors: Schmitt, Manuel, Mayländer, Maximilian, Heizmann, Tim, Richert, Sabine, Bülow, Christine, Hirsch, Konstantin, Zamudio‐Bayer, Vicente, Lau, J. Tobias, Krossing, Ingo
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 12-12-2022; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: Arene Ligands; Benzene; Cations; Communication; Communications; Magnetic properties; Nickel; Nickel carbonyl; NMR; Nuclear magnetic resonance; Oxidation; Sandwich Complexes; Sandwich structures; Single crystals; Transition Metals; Vapor phases; Weakly Coordinating Anion (WCA); Weakly Coordinating Anion (WCA); Nickel; Transition Metals; Sandwich Complexes; Arene Ligands
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202211555

A stable salt of the metalloradical [Ni(C6H6)2]+ hitherto unknown in the condensed phase was synthesized from [Ni(CO)4]+[WCA]− and benzene ([WCA]−=[F{Al(ORF)3}2]−; RF=C(CF3)3). Single crystal XRD reveals a remarkable asymmetrically η3,η6‐slipped sandwich structure. The magnetic properties of the [Ni(C6H6)2]+ cation were determined in solution and in the gas phase. Oxidation with the synergistic Ag+/0.5 l2 system led to the salt [Ni(C6H6)2]2+([WCA]−)2. All products were fully characterized by means of IR, Raman, NMR/EPR, single crystal and powder XRD.
The metalloradical [Ni(C6H6)2]+, hitherto unknown in the condensed phase, was synthesized from [Ni(CO)4]+[WCA]− and benzene ([WCA]−=[F{Al(ORF)3}2]−; RF=C(CF3)3). The [Ni(C6H6)2]+ cation exhibits an asymmetric slipped sandwich structure. Its magnetic properties were determined in solution and in the gas phase. Further oxidation with the Ag+/0.5 l2 system led to the salt [Ni(C6H6)2]2+([WCA]−)2.