The role of proton-coupled electron transfer in O—O bond activation

INOR 85

Joel Rosenthal, jr330@mit.edu and Daniel G. Nocera, nocera@mit.edu. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave, Room 18-444, Cambridge, MA 02139
The selective reduction of oxygen to water requires four electrons and four protons. The design of catalysts that promote oxygen-water interconversion need to manage both electron and proton inventories. Pacman and Hangman porphyrins architectures have proven to be well suited catalysts for such PCET processes, providing a cleft for oxygen binding, a redox shuttle for oxygen reduction and functionality to tune the acid-base properties of bound oxygen and its intermediates. With proper control of the proton-coupled electron transfer events, O—O bond breaking of oxygen, may be achieved with high efficiencies.