Atomically Precise NanoClusters (APNCs) are an emerging class of materials with a broad scope of applications ranging from imaging to medicine. Despite numerous methodologies for the preparation of APNCs of precious metals, there remains a paucity of comparable APNCs based on copper, an environmentally benign, low cost, and earth abundant metal. In part, this can be attributed to a lack of convenient and reproduceable methodologies to access them. Indeed, due to weak cuprophilic interactions, current methodologies tend to produce ill-defined, polydisperse mixtures.<br/><br/>Our group has shown that the electronic and steric properties of cyclic(alkyl)(amino)carbenes (CAACs) are well-suited for the stabilization of low valent monomeric copper (0). Capitalizing on these results, we envisaged an innovative strategy to access low valent APNCs of copper and wish to report on the preparation of a well-defined trinuclear mixed-valent copper (0)/(I) cluster stabilized by CAACs. This result constitutes an exceedingly rare example of a copper APNC with predominately copper (0) character and has engendered unprecedented reactivity including towards small molecules. We believe that our methodology opens new avenues in the synthesis of well-defined, reproducible copper APNCs and can be extended to a variety of other metals.

Synthesis and reactivity of a well-defined mixed-valent copper (0)/(I) nanocluster

2019 Fall National Meeting

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