Synthesis of tetranuclear rhenium(i) tricarbonyl metallacycles

Re(i) tricarbonyl complexes have received much attention due to their attractive photochemical, electrochemical, and biological properties. Beyond simple mononuclear complexes, multinuclear assemblies offer greater structural diversity and properties. Despite previous reports on the preparation of di-, tri-, or tetranuclear Re(i) tricarbonyl assemblies, the synthesis of these supramolecular structures remains challenging due to overall low yields or tedious purification protocols. Herein, the facile preparation and characterization of tetranuclear Re(i) tricarbonyl metallacycles with a square geometry is reported using a tetrazole-based ligand. The synthesis of the metallacycle was optimized using different metal precursors, solvents, temperatures, and reagent concentrations. Finally, the scope of suitable tetrazole-based ligands was explored to produce several tetranuclear Re(i) tricarbonyl-based metallacycles.