Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier, CNRS, 118 Route de Narbonne, 31062, Toulouse, France.
Univ Lyon, ENS Lyon, CNRS, Universite Lyon 1, Laboratoire de Chimie, UMR 5182, 46 allée d'Italie, 69364, Lyon, France.
Angew Chem Int Ed Engl. 2023 Jan 16;62(3):e202209102. doi: 10.1002/anie.202209102. Epub 2022 Dec 13.
Ammonia, NH , is an essential molecule, being part of fertilizers. It is currently synthesized via the Haber-Bosch process, from the very stable dinitrogen molecule, N and dihydrogen, H . This process requires high temperatures and pressures, thereby generating ca 1.6 % of the global CO emissions. Alternative strategies are needed to realize the functionalization of N to NH under mild conditions. Here, we show that boron-centered radicals provide a means of activating N at room temperature and atmospheric pressure whilst allowing a radical process to occur, leading to the production of borylamines. Subsequent hydrolysis released NH , the acidic form of NH . EPR spectroscopy supported the intermediacy of radicals in the process, corroborated by DFT calculations, which rationalized the mechanism of the N functionalization by R B radicals.
氨，NH3，是一种基本分子，是肥料的组成部分。目前，它是通过哈伯-博世工艺由非常稳定的氮气分子 N2 和氢气 H2 合成的。该过程需要高温高压，因此产生了全球约 1.6%的二氧化碳排放。需要替代策略来实现温和条件下的氮向氨的功能化。在这里，我们表明硼中心自由基为在室温常压下激活 N 提供了一种方法，同时允许自由基过程发生，导致硼胺的生成。随后的水解释放出氨，即 NH3 的酸性形式。电子顺磁共振（EPR）光谱支持该过程中自由基的中间体存在，这得到了密度泛函理论（DFT）计算的证实，该计算合理化了 R B 自由基对 N 官能化的机理。
