The conformationally flexible tetradentate pyridinophane ligand (tBu)N4 effectively lowers the oxidation potential of ((tBu)N4)PdII complexes and promotes their facile chemical and electrochemical oxidation, including unpredecented aerobic oxidation reactivity. While the low potential of a number of PdII (and PtII) complexes supported by various fac-chelating polydentate ligands is often attributed to the presence of a coordinating group in the axial position of the metal center, no detailed electrochemical studies have been reported for such systems. Described herein is the detailed electrochemical investigation of the effect of ligand conformation on the redox properties of the corresponding PdII complexes. These Pd complexes adopt different conformations in solution, as supported by studies using variable scan rate, variable-temperature cyclic voltammetry (CV), differential pulse voltammety, and digital CV simulations at variable scan rates. The effect of the axial amine protonation on the spectroscopic and electrochemical properties of the complexes was also investigated. A number of new PdIII complexes were characterized by electron paramagnetic resonance, UVvis spectroscopy, and X-ray diffraction including [((tBu)N4)(PdCl2)-Cl-III]ClO4, a dicationic [((tBu)N4)(PdMe)-Me-III(MeCN)](OTf)(2), and an unstable tricationic [((tBu)N4)Pd-III(EtCN)(2)](3+) species. Although the electron-rich neutral complexes ((tBu)N4)PdMeCl and ((tBu)N4)PdMe2 are present in solution as a single isomer with the axial amines not interacting with the metal center, their low oxidation potentials are due to the presence of a minor conformer in which the (tBu)N4 ligand adopts a tridentade (kappa(3)) conformation. In addition, the redox properties of the ((tBu)N4)Pd complexes show a significant temperature dependence, as the low-temperature behavior is mainly due to the contribution from the major, most stable conformer, while the room-temperature redox properties are due to the formation of the minor, more easily oxidized conformer(s) with the (tBu)N4 ligand acting as a tridentate (kappa(3)) or tetradentate (kappa(4)) ligand. Overall, the coordination to the metal center of each axial amine donor of the tBuN4 ligand leads to a lowering of the Pd-II/(III) oxidation potential by similar to 0.6 V. These detailed electrochemical studies can thus provide important insights into the design of new ligands that can promote Pd-catalyzed oxidation reactions employing mild oxidants such as O-2.