Biological systems utilize multicopper clusters to activate small molecule substrates, such as nitrous oxide by CuZ in nitrous oxide reductase, and dioxygen by the tri-copper clusters in multicopper oxidases. These reactions consitute a rich area of active research with potential implications in greenhouse gas mitigation and in green energy technologies (e.g., as ORR catalysts). In this context, we have been exploring the reactivity of a designed tricopper(I) compound housed within a anionic cyclophane (or cyclophanate in reference to cryptand and cryptate). We have previously communicated the coordination of dinitrogen within the all cuprous complex as well as its conversion to a µ3-sulfidotricopper complex. Here, our recent efforts to understand the electronic structure of this and the related oxo- and selenido-bridged compounds will be discussed, with particulat reference to our understanding and covalency and charge delocalization this series. The consequence of this electronic structure description is borne out in the reactivity of this chalcogen-bridged series of compounds as well as of the tricopper(I)-dinitrogen species with O2.

Tale of bonding and reactivity by tricopper cyclophanates

254th National Meeting (2017)

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