Ni‐Mediated High‐Spin Iron(III) for Boosting Electrocatalytic NO to Oxime Conversion

Abstract

Abstract Oximes serve as indispensable intermediates in synthetic chemistry, owing to their distinctive C═N─OH structure, conferring highly versatile reactivity. Synthesis of oxime via the electrochemical method has potential advantages, accompanied by the upgrading of industrialization. Herein, we propose a novel strategy by introducing nickel (Ni) mediation to obtain high‐spin iron (Fe)(III) in phthalocyanine structure for synthesizing glyoxylate oxime via electrocatalytic nitric oxide (NO) coupling with keto acid. The optimized pFeNiPc catalyst achieved a Faradaic efficiency of 84.3% and a long‐term stability for glyoxylate oxime electrosynthesis. Moreover, the oxime could be directly cyclized to synthesize a gram‐level agrochemical isoxazoline molecule. The enriched amounts of high‐spin Fe(III) sites promote the accumulation of NO on the catalyst surface and further accelerate reduction, which enables the efficient adsorption‐conversion of NO to oxime. This work devises an innovative strategy to selectively engineer the activation of catalytic sites by tailoring electronic configuration and presents a method to facilitate NO valorization in organonitrogen synthesis.