3 years ago

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

Transient Formation and Reactivity of a High-Valent Nickel(IV) Oxido Complex
Marcel Swart, Gloria Primi, Davide Angelone, Moniek Tromp, Apparao Draksharapu, Sandeep K. Padamati, Wesley R. Browne, David J. Martin
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.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b04158

DOI: 10.1021/jacs.7b04158

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