1. Redox Coupling for Multielectron Small-Molecule Activation
Jake D. Soper
School of Chemistry and Biochemistry, Georgia Institute of Technology
901 Atlantic Drive NW, Atlanta, GA
The ability to make and break bonds with a high degree of specificity has applications ranging from benchtop synthesis to the conversion of solar energy into clean chemical fuels. Selectivity in transformations of small-molecule substrates is predicated on the ability to transfer multiple electrons in a single step. We are developing new catalysts based on inexpensive, naturally-abundant later first-row transition metals as surrogates for current state-of-the-art inorganic catalysts for multielectron bond-making and bond-breaking reactions, which are typically very expensive.
Our approach to this problem utilizes redox-active ligands to store and deliver charge to later 3d metal centers for multielectron reactions with small molecules. For instance, in the reaction above, the 2e– activation of dichloromethane occurs without a change in oxidation state at the cobalt(III) center. This reaction forms the basis for new cross coupling catalysis cycles for C–C, C–N and C–O bond-forming reactions at sp3-hybridized carbon centers.