van IJzendoorn Bono, Lister-Roberts Reece, Kaltsoyannis Nikolas, Mehta Meera
Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford OX1 3QR, U.K.
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
J Am Chem Soc. 2025 Aug 20;147(33):30317-30325. doi: 10.1021/jacs.5c09618. Epub 2025 Aug 6.
Nitrous oxide (NO) is sometimes referred to as the forgotten greenhouse gas, but ignoring it would be a mistake. NO has a greenhouse warming potential 300× that of CO, and anthropogenic emissions are increasing. Yet, compared to CO, homogeneous catalysts that mediate its reduction are scarce. We present a range of cluster catalysts based on abundant and inexpensive p-block elements that mediate the conversion of NO to environmentally benign N. The catalysts studied offer many critical advantages, and systems can be tuned for performance, recyclability, selectivity, air stability, and commercial availability. Pnictogen clusters present themselves as a general platform in NO reduction chemistry, and control reactions confirm that these clusters offer access to reactivity that simple monopnictogen molecules do not. Mechanistic investigations reveal that the low-valent clusters can access a -1/+1 redox couple, which goes beyond classical main group redox couples and will unlock a vault of hitherto unknown chemical space.
一氧化二氮（N₂O）有时被称为被遗忘的温室气体，但忽视它将是一个错误。N₂O的温室变暖潜能是CO₂的300倍，且人为排放量正在增加。然而，与CO₂相比，介导其还原的均相催化剂却很稀少。我们展示了一系列基于丰富且廉价的p区元素的簇催化剂，它们介导N₂O转化为环境友好的N₂。所研究的催化剂具有许多关键优势，并且可以针对性能、可回收性、选择性、空气稳定性和商业可用性进行调整。氮族元素簇在N₂O还原化学中呈现为一个通用平台，对照反应证实这些簇提供了简单单氮族元素分子所不具备的反应活性。机理研究表明，低价簇可以进入-1/+1氧化还原对，这超越了经典的主族氧化还原对，将开启一个迄今为止未知的化学空间宝库。
