Molecular nitrogen (N₂), an abundant component of the atmosphere, is appealing for industrial value‐added products. However, its intrinsic inertness limits its activation to mainly metallic species. Environmental concerns and harsh reaction conditions have resulted in a demand for alternate nonmetallic and nontoxic routes to activate and functionalize N₂ at ambient conditions. Comprehensive density functional theory (DFT) calculations are performed on N₂ activation by boron species, specifically for the experimentally more accessible tricoordinated boron compounds. Subsequently designed frustrated Lewis pairs (FLPs) combining screened N‐heterocyclic carbene with boron moieties can make N₂ activation both kinetically and thermodynamically favorable, displaying high potential for metal‐free N₂ activation. The significant thermodynamic stability of the products stabilized by aromaticity and low activation barriers could be a breakthrough for the development of FLP chemistry on metal‐free N₂ activation.

中文翻译：

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三配位硼物种对二氮的活化作用：系统设计

分子氮（N ₂）是大气中的重要组成部分，正吸引着工业增值产品。然而，其固有的惰性将其活化限制为主要是金属物质。对环境的关注和苛刻的反应条件导致对在环境条件下活化和官能化N _2的非金属和无毒替代路线的需求。全面的密度泛函理论（DFT）计算是针对硼物种对N _2的活化而进行的，特别是针对实验上更易获得的三配位硼化合物。随后设计的沮丧的刘易斯对（FLP）将筛选出的N杂环卡宾与硼部分相结合可以使N ₂活化在动力学和热力学上都具有优势，显示出无金属N ₂活化的潜力。通过芳香性和低活化势垒稳定的产品具有显着的热力学稳定性，这可能是无金属N ₂活化FLP化学发展的突破。