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Keywords:

  • electron transfer;
  • isomers;
  • proton reduction;
  • ruthenium;
  • water oxidation
Thumbnail image of graphical abstract

Basic difference: The importance of a pendent base in promoting proton-coupled electron-transfer reactions with low activation barriers has been discussed for H+ reduction or H2 oxidation in acetonitrile. Investigation of the interaction between a base positioned in the second coordination sphere of a complex and a water ligand in water oxidation reactions using geometric isomers of [Ru(tpy)(pynap)(OH2)]2+ (see picture) gave intriguing results.