Intramolecular Electrostatic Effects on O2 , CO2 , and Acetate Binding to a Cationic Iron Porphyrin

Inorganic Chemistry
Daniel J MartinJames M Mayer

Abstract

Noncovalent electrostatic interactions are important in many biological and chemical reactions, especially those that involve charged intermediates. There has been a growing interest in using electrostatic ligand designs-placing charges in the second coordination sphere-to improve molecular reactivity, catalysis, and electrocatalysis. For instance, an iron porphyrin bearing four cationic ortho-trimethylanilinium groups, Fe(o-TMA), has been reported to be an exceptional electrocatalyst for both the carbon dioxide reduction reaction (CO2RR) and the oxygen reduction reaction (ORR). These reactions involve many different steps, and it is not evident which steps are affected by the four positive charges, or why. By comparing Fe(o-TMA) with the related iron-tetraphenylporphyrin, this work examines how covalently positioned charged groups affect substrate binding and other key pre-equilibria of both the ORR and CO2RR, specifically acetate, dioxygen, and carbon dioxide binding. This study is among the first to directly measure the effects of electrostatics on ligand-binding. The results show that adding electrostatic groups to a catalyst design often results in a complex interplay of multiple effects, including changes in pre-equilibri...Continue Reading

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