Nickel dioxygen chemistry has garnered significant interest by the scientific community due to its catalytic potential and the recent discovery that it plays a role in the enzymatic activity of quercetin 2,4-dioxygenase. This enzyme possesses the ability to use nickel as the active site cofactor to interact with dioxygen in a side-on orientation leading to cleavage and release of the flavanol natural product. The catalytic potentials of nickel-dioxygen adducts are less established by comparison to earth abundant metals such as copper or iron with rich O2 activation chemistry. To continue gaining insight in unraveling the mysteries of nickel dioxygen chemistry in nature, novel ligands that are able to stabilize and tune nickel-(di)oxygen adducts are being developed. Novel N4 macrocycles are being synthesized that interact with H2O2 at a monovalent reaction center to form a 1:1 nickel dioxygen adduct that then undergoes O-O bond cleavage. Detailed analysis and characterization of the resulting metal-(di)oxygen adduct is underway, including the capability of this species to facilitate organic transformations. Through numerous techniques, including UV/vis, FTIR, EPR, rR, ESI-MS, CV, NMR and XRD, mechanistic information has been gained from identification of the pathway of Ni/O2 adduct formation, deciphering the O2 bond cleavage and/or O2 release route, to the elucidation of their catalytic potentials. New ligand analogs and attempts to target precise reactivity will be discussed as well as novel methodologies for promoting nickel-mediated reaction chemistry.

Engineering a potent nickel dioxygen catalyst

254th National Meeting (2017)

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