Affiliation:
1. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.
Abstract
Electrocatalytic approaches to the activation of unsaturated substrates
via reductive concerted proton-electron transfer (CPET) must overcome
competing, often kinetically dominant hydrogen evolution. We introduce the
design of a molecular mediator for electrochemically triggered reductive
CPET through the synthetic integration of a Brønsted acid and a redox
mediator. Cathodic reduction at the cobaltocenium redox mediator
substantially weakens the homolytic nitrogen-hydrogen bond strength of a
Brønsted acidic anilinium tethered to one of the cyclopentadienyl rings. The
electrochemically generated molecular mediator is demonstrated to transform
a model substrate, acetophenone, to its corresponding neutral α-radical via
a rate-determining CPET.
Funder
U.S. Department
of Energy
Publisher
American Association for the Advancement of Science (AAAS)
Cited by
87 articles.
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