Transient Formation and Reactivity of a High-Valent Nickel(IV) Oxido Complex

A reactive high-valent dinuclear nickel(IV) oxido bridged complex is reported that can be formed at room temperature by reaction of [(L)₂Ni(II)₂(μ-X)₃]X (X = Cl or Br) with NaOCl in methanol or acetonitrile (where L = 1,4,7-trimethyl-1,4,7-triazacyclononane). The unusual Ni(IV) oxido species is stabilized within a dinuclear tris-μ-oxido-bridged structure as [(L)₂Ni(IV)₂(μ-O)3]²⁺. Its structure and its reactivity with organic substrates are demonstrated through a combination of UV–vis absorption, resonance Raman, ¹H NMR, EPR, and X-ray absorption (near-edge) spectroscopy, ESI mass spectrometry, and DFT methods. The identification of a Ni(IV)-O species opens opportunities to control the reactivity of NaOCl for selective oxidations.