Rouf Alvi Muhammad, Huang Yuanyuan, Dong Shicheng, Zhu Jun
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
Inorg Chem. 2021 Apr 19;60(8):5598-5606. doi: 10.1021/acs.inorgchem.0c03520. Epub 2021 Mar 31.
Activation of atmospherically abundant dinitrogen (N) by metal-free species under mild reaction conditions has been one of the most challenging areas in chemistry for decades. Very recent but limited progress in N activation by boron species, including two-coordinated borylene and methyleneborane and three-coordinated borole and borane, has been made toward metal-free N activation. Here, we systematically probe an experimentally viable frustrated Lewis pair (FLP) containing two moieties (methyleneborane and carbene) for N activation via density functional theory (DFT) calculations, which has proven to be an efficient approach for N activation in a thermodynamically and kinetically favorable manner. Aromaticity is found to play a crucial role in stabilization of the product. This study could be a valuable alternative for the development of metal-free N activation chemistry, highlighting great potential of FLP for N activation and functionalization.
几十年来，在温和反应条件下通过无金属物种激活大气中丰富的二氮（N）一直是化学领域最具挑战性的领域之一。最近，包括二配位硼烯和亚甲基硼烷以及三配位硼杂环戊二烯和硼烷在内的硼物种在氮活化方面取得了有限但非常新的进展，朝着无金属氮活化方向发展。在这里，我们通过密度泛函理论（DFT）计算系统地探索了一种实验上可行的、包含两个部分（亚甲基硼烷和卡宾）的受阻路易斯对（FLP）用于氮活化，这已被证明是以热力学和动力学有利的方式进行氮活化的有效方法。发现芳香性在产物的稳定化中起关键作用。这项研究可能是无金属氮活化化学发展的一个有价值的替代方案，突出了FLP在氮活化和功能化方面的巨大潜力。
