AbstractThe production of stable phenoxyl radicals is undoubtedly a synthetic chemical challenge. Yet it is a useful way to gain information on the properties of the biological tyrosyl radicals. Recently, several persistent phenoxyl radicals have been reported, but only limited synthetic variations could be achieved. Herein, we show that the amide–o‐substituted phenoxyl radical (i.e. with a salicylamide backbone) can be synthesised in a stable manner, thereby permitting easy synthetic modifications to be made through the amide bond. To study the effect of H‐bonding on the properties of the phenolate/phenoxyl radical redox couple, simple H‐bonded and non‐H‐bonded o,p‐tBu‐protected salicylamidate compounds have been prepared. Their redox properties were examined by cyclic voltammetry and showed a fully reversible one‐electron oxidation process to the corresponding phenoxyl radical species. Remarkably, the redox potential appears to be correlated, at least partially, with H‐bond strength, as relatively large differences (ca. 300 mV) in the redox potential between H‐bonded and non‐H‐bonded phenolate salts are observed. The corresponding phenoxyl radicals produced electrochemically are persistent at room temperature for at least an hour; their UV/Vis and EPR characterisation is consistent with that of phenoxyl radicals, which makes them excellent models of biological tyrosyl radicals. The analyses of the experimental data coupled with theoretical calculations indicate that both the deviation from planarity of the amide function and intramolecular H‐bonding influence the oxidation potential of the phenolate. The latter H‐bonding effect appears to be predominantly exerted on the phenolate and not (or only a little) on the phenoxyl radical. Thus, in these systems the H‐bonding energy involved in the phenoxyl radical appears to be relatively small.