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

@article{Sjdin2006KineticEO,
  title={Kinetic effects of hydrogen bonds on proton-coupled electron transfer from phenols.},
  author={Martin Sj{\"o}din and Tania Irebo and Josefin E. Utas and Johan Lind and G{\'a}bor Mer{\'e}nyi and Bj{\"o}rn {\AA}kermark and Leif Hammarstr{\"o}m},
  journal={Journal of the American Chemical Society},
  year={2006},
  volume={128 40},
  pages={
          13076-83
        }
}
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… Expand
Kinetic effects of increased proton transfer distance on proton-coupled oxidations of phenol-amines.
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TLDR
The relationship between the structural and spectroscopic properties of the phenols and their CPET reactivity is discussed, and compounds with electron-withdrawing substituents have significantly lower reactivity. Expand
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Multiple-site concerted proton-electron transfer reactions of hydrogen-bonded phenols are nonadiabatic and well described by semiclassical Marcus theory.
TLDR
Results for the oxidation of HOAr-Py, in which the phenol and base are conjugated, and for oxidation of 2,4,6-(t)Bu(3)C(6)H(2)OH, which lacks a base, show that both have substantially lower λ and larger pre-exponential terms, a very clear demonstration that the reactions are nonadiabatic. Expand
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