Enhanced Ammonia Oxidation Catalysis by a Low-Spin Iron Complex Featuring Cis Coordination Sites

Abstract

The goal of using ammonia as a solar fuel motivates the development of selective ammonia oxidation (AO) catalysts for fuel cell applications. Herein, we describe Fe-mediated AO electrocatalysis with [(bpyPy₂Me)Fe(MeCN)₂]²⁺, exhibiting the highest turnover number (TON) reported to date for a molecular system. To improve on our recent report of a related iron AO electrocatalyst, [(TPA)Fe(MeCN)₂]²⁺ (TON of 16), the present [(bpyPy₂Me)Fe(MeCN)₂]²⁺ system (TON of 149) features a stronger-field, more rigid auxiliary ligand that maintains cis-labile sites and a dominant low-spin population at the Fe(II) state. The latter is posited to mitigate demetalation and hence catalyst degradation by the presence of a large excess of ammonia under the catalytic conditions. Additionally, the [(bpyPy₂Me)Fe(MeCN)₂]²⁺ system exhibits a substantially faster AO rate (ca. 50×) at significantly lower (∼250 mV) applied bias compared to [(TPA)Fe(MeCN)₂]²⁺. Electrochemical data are consistent with an initial E₁ net H-atom abstraction step that furnishes the cis amide/ammine complex [(bpyPy₂Me)Fe(NH₂)(NH₃)]²⁺, followed by the onset of catalysis at E₂. Theoretical calculations suggest the possibility of N–N bond formation via multiple thermodynamically plausible pathways, including both reductive elimination and ammonia nucleophilic attack. In sum, this study underscores that Fe, an earth-abundant metal, is a promising metal for further development in metal-mediated AO catalysis by molecular systems.