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Published on: November 21, 2017
Generation and Reactivity of a NiIII2(μ-1,2-peroxo) Complex
Norman Zhao1, Alexander S Filatov1, Jiaze Xie1
1Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Abstract:
High-valent transition metal-oxo, -peroxo, and -superoxo complexes are crucial intermediates in both biological and synthetic oxidation of organic substrates, water oxidation, and oxygen reduction. While high-valent oxygenated complexes of Mn, Fe, Co, and Cu are increasingly well-known, high-valent oxygenated Ni complexes are comparatively rarer. Herein we report the isolation of such an unusual high-valent species in a thermally unstable NiIII2(μ-1,2-peroxo) complex, which has been characterized using single-crystal X-ray diffraction and X-ray absorption, NMR, and UV-vis spectroscopies. Reactivity studies show that this complex is stable toward dissociation of oxygen but reacts with simple nucleophiles and electrophiles.
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