Electrochemical Oxidation of Organic Molecules at Lower Overpotential: Accessing Broader Functional Group Compatibility with Electron−Proton Transfer Mediators

ConspectusElectrochemical organic oxidation reactions are highly appealing because protons are often effective terminal electron acceptors, thereby avoiding undesirable stoichiometric oxidants. These reactions are often plagued by high overpotentials, however, that greatly limit their utility. Single-electron transfer (SET) from organic molecules generates high-energy radical-cations. Formation of such intermediates often requires electrode potentials far above the thermodynamic potentials of the reaction and frequently causes decomposition and/or side reactions of ancillary functional groups. In this Account, we show how electrocatalytic electron–proton transfer mediators (EPTMs) address this challenge. EPTMs…

• NS
  National Science Foundation

  Awards: 1305124, DE-SC0018409, CHE-1305124
• UD
  U.S. Department of Energy

  Awards: FC02-07ER64494, 07ER64494, DE-FC02-07ER64494, FG02-05ER15690, DE-FG02-05ER15690, SC0018409, DE-SC0018409, DE-FG02-, DE-FG02
• M
  Merck
• A
  AbbVie
• NI
  National Institutes of Health

  Award: R01 GM100143
• OO
  Office of Science

  Awards: DE-FC02-07ER64494, DE-SC0018409
• GL
  Great Lakes Bioenergy Research Center

  Awards: DE-SC0018409, DE-FC02-07ER64494
• NI
  National Institute of General Medical Sciences

  Award: R01 GM100143
• DO
  Division of Chemistry

  Awards: 1305124, CHE-1305124
• BE
  Basic Energy Sciences

  Award: DE-FG02-05ER15690