Using a bioinspired approach, nickel(I) complexes that activate dioxygen have been systematically interrogated.  Advanced spectroscopic methods, coupled with single crystal X-ray diffraction, when available, have led to a detailed understanding of the electronic and geometric structures of intermediates.  In addition to ascertaining the identity of these intermediates, this presentation will address the efficacy of a new superoxo-nickel(II) to activate substrate C–H bonds.  The superoxo-nickel(II) species activation of dihydroanthracene (and xanthene, cyclohexadiene) involves formation of a hydroperoxy-nickel(II) intermediate that has been prepared independently.  Subsequent O–O bond rupture entails intramolecular activation of a high energy C–H bond on a ligand <i>tert</i>-butyl substituent.  Mechanistic details will be presented.<br/>

C–H activation by a discrete superoxonickel complex

253rd National Meeting (2017)

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