Synthesis and structural characterization of mono- and bimetallic azodioxide complexes of first-series transition metals

• Published in: Inorganica Chimica Acta 2025-01, Vol.574, p.122354, Article 122354
• Main Authors: Salem, Ahmed M.H., Hussein, Dina S., Terkawi, Sara S., Stratton, Audrey N., Chen, Wei-Yuan, Schrage, Briana R., Emhoff, Kylin A., Tate, Masai M., Minerovic, Grace M., Ziegler, Christopher J., Boyd, W. Christopher
• Format: Article
• Language: English
• Subjects: Azodioxide; Copper; Manganese; Nickel; Octahedral coordination; Trigonal prismatic coordination
• ISSN: 0020-1693
• DOI: 10.1016/j.ica.2024.122354

[Display omitted] •Five new azodioxide complexes have been prepared and characterized.•The number of structurally characterized complexes of this ligand has been doubled.•The coordination geometry at the metal center varies widely. The treatment of metal chlorides MCl2 or metal chlorido complexes M(bpy)Cl2 (M = Mn, Ni, Cu, bpy = 2,2′-bipyridyl) with TlPF6 in acetonitrile to precipitate TlCl, followed by addition of excess nitrosobenzene, yielded monometallic or bimetallic azodioxide complex salts of the form [M(az)4](PF6)2, [M(bpy)2(az)](PF6)2, and [{M(bpy)(az)(μ-Cl)}2](PF6)2 (az = cis-N,N′-diphenylazodioxide), which have been structurally characterized via single-crystal X-ray diffraction. The method of activation of chloride salts or chlorido complexes by chloride abstraction with Tl+, followed by the addition of nitrosobenzene, continues to be an effective strategy for the synthesis of azodioxide complexes, and it has enabled the synthesis of the first structurally characterized azodioxide complexes of any metals of Groups 7, 10, or 11.