Nitric oxide reduction yielding N₂O is known as a route to detoxify nitric oxide (NO) to relieve nitrosative stress in pathogenic bacteria and fungi. Nitric oxide enzymes are classified into Cu/Fe‐heme NO reductases (NORs) and non‐heme flavindiiron NO reductases (FNORs). In biological system, the mechanism of NO reduction generating N₂O was proposed to involve NO coordination to metal centers prior to producing cis/trans‐hyponitrite‐bound intermediate, and the subsequent protonation of hyponitrite‐bound‐Fe/Cu intermediates releases N₂O. In this review article, we compile the recently published biomimetic model studies of NO‐to‐[N₂O₂]²⁻ transformation triggered by the designed transition‐metal complexes. In biomimetic model study, the ON‐NO bond coupling of metal‐nitrosyl complexes yielding [N₂O₂]²⁻‐bound species may occur via either the inter/intramolecular radical‐[NO]⁻‐radical‐[NO]⁻ coupling or metal‐[NO]²⁻ radical coupling with exogenous NO˙. The H‐bonding interaction between hyponitrite and protic solvents promoting/stabilizing the formation of hyponitrite complexes was also demonstrated. In addition, the electronic structure of the designed transition‐metal‐nitrosyl complexes triggering the formation of [N₂O₂]²⁻‐bound species and the detailed NO‐to‐[N₂O₂]²⁻ formation pathways were delineated.

中文翻译：

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含金属配合物触发的一氧化氮还原反应形成亚硝酸盐

产生N ₂ O的一氧化氮还原被认为是对一氧化氮（NO）进行解毒以缓解病原细菌和真菌中亚硝化胁迫的一种途径。一氧化氮酶分为铜/铁血红素NO还原酶（NORs）和非血红素黄素二铁NO还原酶（FNORs）。在生物系统中，提出了NO还原生成N ₂ O的机制，涉及在生成顺式/反式与亚铁盐结合的中间体之前，先与金属中心进行NO配位，随后与亚硝酸盐结合的Fe / Cu中间体的质子化会释放N _2。 O.在这篇评论文章中，我们汇编了最近发表的NO至[N ₂ O ₂ ] ^2−的仿生模型研究由设计的过渡金属配合物触发的转变。在仿生模型研究中，金属亚硝酰基配合物的ON-NO键偶联，得到[N ₂ Ò ₂ ] ^2-可经由帧间/分子内自由基发生结合的物种[NO] ^- -radical- [NO] ^-耦合或金属[NO] ^2-自由基与外源NO˙的偶联。还证明了亚硝酸盐与质子溶剂之间的氢键相互作用促进/稳定了亚硝酸盐络合物的形成。此外，设计的过渡金属-亚硝酰基配合物的电子结构会触发[N ₂ O ₂ ] ^2-的形成。描绘了结合的物种和详细的NO- [N ₂ O ₂ ] ²⁻形成途径。