The preparation of the facial and meridional isomers of [Ir(pyalk)(3)] (pyalk = 2-(2-pyridyl)isopropanoate), as model complexes for a powerful water oxidation catalyst, is reported. The strongly donating N3O3 ligand set is very oxidation-resistant, yet promotes facile metal-centered oxidation to form stable Ir(IV) compounds. The Ir-III/IV reduction potentials of the two isomers differ by 340 mV despite the identical ligand set. A ligand field rationalization is advanced and supported by DFT calculations.