Rational Optimization of Self‐Reporting Alcohol‐Oxidizing RhIII$^{\mathrm{III}}$ Complexes

Understanding (photo)chemical extraction of reducing equivalents from surrounding media is indispensable for optimizing coupled redox catalysis. Exploiting the optical self‐reporting property of a variety of ‐diimine‐coordinated Rh(Cp*) complexes upon chemical reduction by isopropanol, structure–activity‐correlations could be found. This leads to an optimization of this process with respect to pH, temperature, complex concentration, and additives. Electron withdrawing groups at the ‐diimine ligand allowed for alcohol oxidation at even neutral pH. These results pave the way to optimized utilization of Rh(Cp*) complexes in artificial photosynthesis schemes.