Metal clusters, either as minimal fragments of extended solids or as discrete assemblies within metalloprotein active sites, catalyze synthetically-challenging multi-proton and multi-electron redox reactions, such as N2 and CO2 activation. Common to the proposed reaction mechanisms is the redox cooperativity afforded by multiple transition metal ions. To understand the structural and electronic factors that govern redox cooperativity, we explore the use of rationally-designed macrobicyclic ligands to template the assembly of multimetallic complexes and present the synthesis of a series of 3d- and main-group macrobicyclic clusters. Ongoing reactivity studies of the hydride-containing and reduced complexes with unsaturated substrates and the impact of preorganization on redox cooperativity will be discussed.

Macrobicyclic approach for harnessing redox cooperativity in multimetallic assemblies

247th National Meeting (2014)

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