Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, 02139, USA.
Institute of Chemical Research of Catalonia, The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
Angew Chem Int Ed Engl. 2021 Mar 29;60(14):7845-7850. doi: 10.1002/anie.202015359. Epub 2021 Mar 1.
Dianionic hyponitrite (N O ) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme-copper oxidases and nitric oxide reductases. In this work, we examine the gas-solid reaction of nitric oxide with the metal-organic framework Cu -ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N O intermediate. These results highlight the advantage provided by site-isolation in metal-organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one-electron couple in these enzymes.
二价亚硝根离子（N O ）通常基于模型配合物而被提出，是血红素铜氧化酶和一氧化氮还原酶双金属活性位点上一氧化氮还原为一氧化二氮的关键中间产物。在这项工作中，我们通过一系列原位光谱和密度泛函理论模拟研究了一氧化氮与金属有机骨架 Cu-ZrTpmC*的气固反应，并确定了一种不寻常的螯合 N O 中间产物。这些结果突出了金属有机骨架（MOFs）中位点隔离在研究重要反应中间体方面的优势，并提供了一种与这些酶中提出的单电子对兼容的机理情景。
