Flipped Spin‐State Resists Cobalt Poisoning for the Durable Electrocatalytic Deuteration of N ‐Heterocyclic Compounds

作者：Meng He, Chuanqi Cheng, Haotian Wang, Rui Li, Cuibo Liu, Ying Gao, Bin Zhang · 发表于：Angewandte Chemie International Edition · 年份：2026 · DOI：10.1002/anie.7797032 · 研究领域：Chemical Reactions and Isotopes、Environmental remediation with nanomaterials、Radical Photochemical Reactions

ABSTRACT Electrocatalytic deuteration represents a sustainable method for synthesizing deuterated N ‐heterocycles, which are scaffolds for drug development. However, the utility of this transformation is severely restrained by strong orbital interactions between metal sites and the lone pairs of N atoms that lead to irreversible catalyst deactivation. Here, we propose a Mn 3 Co 7 alloy electrocatalyst that triggers a high‐spin‐to‐low‐spin transition in Co. The flipped spin state originates from tuned d ‐electron pairing, promoting electron occupation in antibonding orbitals and weakening the Co–N bond. The reduced adsorption energy that facilitates the desorption of N ‐heterocycles is revealed to be the key factor driving the improved catalytic durability. This strategy enables a scaled‐up electrosynthesis with a yield of 92.5% at 1.25 A to obtain 10 g of deuterated piperazine hydrochloride. The methodological universality of diverse unsaturated N ‐heterocycles highlights the application potential.