This award in the Inorganic, Bioinorganic, and Organometallic Program supports the work of Dr. Clifford Kubiak of the Chemistry Department, Purdue University, on reduction of carbon dioxide. Organometallic cluster compounds containing three nickel atoms and bridging bis(diphenylphosphino)methane bridging groups have been found to act as photocatalysts for the addition of carbon dioxide to alkenes, and as electrocatalysts for the reduction of carbon dioxide to oxalate. These, as well as newly synthesized, photocatalytic and electrocatalytic systems will be investigated using low temperature photochemistry in matrices, kinetics by laser transient absorption methods, infrared spectroelectrochemistry, and rapid scan voltammetry. Another goal of the project is to elucidate the role of electronic coupling between interconnected metal clusters, and new cluster assemblies in which ligand bond length and electronic properties are systematically varied will be prepared. This research is focused on reactions of carbon dioxide with transition metal complexes. Chemical, photochemical, and electrochemical means will be employed to promote the reduction of carbon dioxide, including reactions in which carbon from this source is bonded to other carbon atoms to form longer carbon chains. These studies are relevant to the problem of finding good uses for carbon dioxide that might be obtained from an atmospheric oversupply.
