The selective 4e^-/4H⁺ reduction of dioxygen to water is an important reaction that takes place at the cathode of fuel cells. Monomeric aromatic tetrapyrroles (such as porphyrins, phthalocyanines, and corroles) coordinated to Co(II) or Co(III) have been considered as oxygen reduction catalysts due to their low cost and relative ease of synthesis. However, these systems have been repeatedly shown to be selective for O₂ reduction by the less desired 2e^-/2H⁺ pathway to yield hydrogen peroxide. Herein, we report the initial synthesis and study of a Co(II) tetrapyrrole complex based on a nonaromatic isocorrole scaffold that is competent for 4e^-/4H⁺ oxygen reduction reaction (ORR). This Co(II) 10,10-dimethyl isocorrole (Co[10-DMIC]) is obtained in just four simple steps and has excellent yield from a known dipyrromethane synthon. Evaluation of the steady state spectroscopic and redox properties of Co[10-DMIC] against those of Co porphyrin (cobalt 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, [Co(TPFPP)]) and corrole (cobalt 5,10,15-tris(pentafluorophenyl)corrole triphenylphosphine, Co[TPFPC](PPh₃)) homologues demonstrated that the spectroscopic and electrochemical properties of the isocorrole are distinct from those displayed by more traditional aromatic tetrapyrroles. Further, the investigation of the ORR activity of Co[10-DMIC] using a combination of electrochemical and chemical reduction studies revealed that this simple, unadorned monomeric Co(II) tetrapyrrole is ∼85% selective for the 4e^-/4H⁺ reduction of O₂ to H₂O over the more kinetically facile 2e^-/2H⁺ process that delivers H₂O₂. In contrast, the same ORR evaluations conducted for the Co porphyrin and corrole homologues demonstrated that these traditional aromatic systems catalyze the 2e^-/2H⁺ conversion of O₂ to H₂O₂ with near complete selectivity. Despite being a simple, easily prepared, monomeric tetrapyrrole platform, Co[10-DMIC] supports an ORR catalysis that has historically only been achieved using elaborate porphyrinoid-based architectures that incorporate pendant proton-transfer groups or ditopic molecular clefts or that impose cofacially oriented O₂ binding sites. Accordingly, Co[10-DMIC] represents the first simple, unadorned, monomeric metalloisocorrole complex that can be easily prepared and shows a privileged performance for the 4e^-/4H⁺ peractivation of O₂ to water as compared to other simple cobalt containing tetrapyrroles.

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