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submitted on 08.04.2020 and posted on 10.04.2020by Norman Zhao, Alexander S. Filatov, Jiaze Xie, Ethan A. Hill, John Anderson
Ni-based oxide materials are promising candidates for catalyzing
the oxygen evolution reaction. The detailed mechanism of water splitting in
these systems has been of interest with a goal of understanding the
intermediate species vital for catalytic activity. A potential intermediate
species prior to release of oxygen is a bridging NiIII2(μ-1,2-peroxo)
complex. However, Ni2(μ-1,2-peroxo) complexes are rare in
general and are unknown with oxidation states higher than NiII.
Herein, we report the isolation of such an unusual high-valent species in a 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. In addition, treatment
with excess tetrabutylammonium chloride results in regeneration of the
species, implicating the reversible release of oxygen or a
reactive oxygen species. Taken together, this suggests that NiIII2(μ-1,2-peroxo)
species are accessible and may be viable intermediates during the oxygen