Electrocatalytic Oxidation of Alcohol with Cobalt Triphosphine Complexes

Spencer P. Heins, Patrick E. Schneider, Amy L. Speelman, Sharon Hammes-Schiffer, Aaron M. Appel

Research output: Contribution to journalArticlepeer-review

14 Scopus citations


Coordination of the tridentate ligand bis(2-diphenylphosphinoethyl)phenylphosphine (P3) to cobalt forms [(CH3CN)2CoIIP3](BF4)2 (CoIIP3). In the presence of the Brönsted base iPr2EtN, CoIIP3 electrocatalytically oxidizes benzyl alcohol (BnOH) to benzaldehyde at an applied potential of -630 mV vs Fc+/0 with a TON of 19.9. In a noncatalytic reaction with excess BnOH and iPr2EtN, CoIIP3 is reduced by one electron to [(CH3CN)2CoIP3]BF4 (CoIP3) with concomitant formation of half an equivalent of benzaldehyde. This stoichiometric oxidation of BnOH suggests electron transfer occurs between intermediate cobalt species and starting CoIIP3. Kinetics and computational studies support an unfavorable alcohol binding preequilibrium step followed by favorable deprotonation of the bound alcohol.

Original languageEnglish (US)
Pages (from-to)6384-6389
Number of pages6
JournalACS Catalysis
Issue number11
StatePublished - Jun 4 2021
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry


  • alcohol oxidation
  • catalysis
  • catalyst design
  • cobalt
  • electrocatalysis
  • electrocatalyst
  • electrooxidation


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