The catalytic sites of nitrous oxide reductase (N2OR) and aerobic carbon monoxide dehydrogenase (CODH) both feature multinuclear copper-sulfide clusters capable of catalytic multielectron redox transformations with small molecule substrates. Because N2OR and CODH play crucial roles in regulating environmental concentrations of the greenhouse gases N2O and CO2, detailed understanding of their chemical properties is of fundamental interest. In this contribution, the synthesis, electronic structure, and reactivity properties of synthetic copper-sulfide model systems will be presented. Included will be discussions of tetranuclear [Cu4S] model systems across three catalytically relevant oxidation states, including the first system that is both a structural and functional mimic of the CuZ active site of N2OR. In addition, the presentation will include reactivity studies of a dinuclear [Cu2S] complex with N2O, CO2, and CS2 that lend insight into one possible role of tetranuclearity of CuZ: protecting the sulfide ligand from oxidation and/or dissociation.

Copper-sulfide clusters that activate nitrous oxide and other small molecules

254th National Meeting (2017)

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