Kinetic effects of hydrogen bonds on proton-coupled electron transfer from phenols

Martin Sjödin, Tania Irebo, Josefin E. Utas, Johan Lind, Gabor Merényi, Björn Åkermark, Leif Hammarström*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

141 Citations (Scopus)


The kinetics and mechanism of proton-coupled electron transfer (PCET) from a series of phenols to a laser flash generated [Ru(bpy)3] 3+ oxidant in aqueous solution was investigated. The reaction followed a concerted electron-proton transfer mechanism (CEP), both for the substituted phenols with an intramolecular hydrogen bond to a carboxylate group and for those where the proton was directly transferred to water. Without internal hydrogen bonds the concerted mechanism gave a characteristic pH-dependent rate for the phenol form that followed a Marcus free energy dependence, first reported for an intramolecular PCET in Sjödin, M. et al. J. Am. Chem. Soc. 2000, 122, 3932-3962 and now demonstrated also for a bimolecular oxidation of unsubstituted phenol. With internal hydrogen bonds instead, the rate was no longer pH-dependent, because the proton was transferred to the carboxylate base. The results suggest that while a concerted reaction has a relatively high reorganization energy (λ), this may be significantly reduced by the hydrogen bonds, allowing for a lower barrier reaction path. It is further suggested that this is a general mechanism by which proton-coupled electron transfer in radical enzymes and model complexes may be promoted by hydrogen bonding. This is different from, and possibly in addition to, the generally suggested effect of hydrogen bonds on PCET in enhancing the proton vibrational wave function overlap between the reactant and donor states. In addition we demonstrate how the mechanism for phenol oxidation changes from a stepwise electron transfer-proton transfer with a stronger oxidant to a CEP with a weaker oxidant, for the same series of phenols. The hydrogen bonded CEP reaction may thus allow for a low energy barrier path that can operate efficiently at low driving forces, which is ideal for PCET reactions in biological systems.

Original languageEnglish
Pages (from-to)13076-13083
Number of pages8
JournalJournal of the American Chemical Society
Issue number40
Publication statusPublished - 2006 Oct 11
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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