德国不莱梅大学Jens Beckmann团队报道了一种稳定结晶亚硝基化合物的合成。相关研究成果于2024年6月13日发表在国际顶尖学术期刊《科学》。

硝基化合物是一类反应性很强但又很基本的化合物。它们具有单价氮原子，通常寿命短，在纳秒范围内。

该文中，研究人员报道了芳基酰胺MSFluindN3(1)光解合成一种稳定的亚硝基化合物，并定量生成芳基亚硝基化合物MSFluindN (2) (MSFluindN = dispiro[芴-9,3 '' -(1 ''，1 ''，7 ''，7 '' -四甲基-s-羟基-4 '' -基)-5 ''，9 '' -芴])，在室温氩气环境下保存至少3天。

超长寿命能够通过单晶X射线晶体学、EPR光谱和SQUID磁强计对2进行全面表征，证明了三重态基态。理论模拟表明，除了庞大的MSF和芳基取代基所赋予的动力学稳定性外，穿过中心芳环的电子离域也有助于2的电子稳定。

附：英文原文

Title: Synthesis of a stable crystalline nitrene

Author: Marvin Janssen, Thomas Frederichs, Marian Olaru, Enno Lork, Emanuel Hupf, Jens Beckmann

Issue&Volume: 2024-06-13

Abstract: Nitrenes are a highly reactive, yet fundamental compound class. They possess a mono-valent nitrogen atom and usually a short life span, typically in the nanosecond range. Here, we report on the synthesis of a stable nitrene by photolysis of the arylazide MSFluindN3 (1), which gave rise to the quantitative formation of the arylnitrene MSFluindN (2) (MSFluind = dispiro[fluorene-9,3′-(1’,1’,7’,7’-tetramethyl-s-hydrindacen-4’-yl)-5′,9’’-fluorene]), that remains unchanged for at least 3 days when stored under argon atmosphere at room temperature. The extraordinary life span permitted the full characterization of 2 by single crystal x-ray crystallography, EPR spectroscopy and SQUID magnetometry, which supported a triplet ground state. Theoretical simulations suggest in addition to the kinetic stabilization conferred by the bulky MSFluind aryl substituent, that electron delocalization across the central aromatic ring contributes to the electron stabilization of 2.

DOI: adp4963

Source: https://www.science.org/doi/10.1126/science.adp4963