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Download fileTransient Formation and Reactivity of a High-Valent Nickel(IV) Oxido Complex
dataset
posted on 2017-06-05, 00:00 authored by Sandeep
K. Padamati, Davide Angelone, Apparao Draksharapu, Gloria Primi, David J. Martin, Moniek Tromp, Marcel Swart, Wesley R. BrowneA 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.
