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.