Abstract

N-containing organic compounds are of vital importance to lives. Practical synthesis of valuable N-containing organic compounds directly from dinitrogen (N₂), not through ammonia (NH₃), is a holy-grail in chemistry and chemical industry. An essential step for this transformation is the functionalization of the activated N₂ units/ligands to generate N−C bonds. Pioneering works of transition metal-mediated direct conversion of N₂ into organic compounds via N−C bond formation at metal-dinitrogen [N₂-M] complexes have generated diversified coordination modes and laid the foundation of understanding for the N−C bond formation mechanism. This review summarizes those major achievements and is organized by the coordination modes of the [N₂-M] complexes (end-on, side-on, end-on-side-on, etc.) that are involved in the N−C bond formation steps, and each part is arranged in terms of reaction types (N-alkylation, N-acylation, cycloaddition, insertion, etc.) between [N₂-M] complexes and carbon-based substrates. Additionally, earlier works on one-pot synthesis of organic compounds from N₂ via ill-defined intermediates are also briefed. Although almost all of the syntheses of N-containing organic compounds via direct transformation of N₂ so far in the literature are realized in homogeneous stoichiometric thermochemical reaction systems and are discussed here in detail, the sporadically reported syntheses involving photochemical, electrochemical, heterogeneous thermo-catalytic reactions, if any, are also mentioned. This review aims to provide readers with an in-depth understanding of the state-of-the-art and perspectives of future research particularly in direct catalytic and efficient conversion of N₂ into N-containing organic compounds under mild conditions, and to stimulate more research efforts to tackle this long-standing and grand scientific challenge.

中文翻译：

---

二氮的直接转化：通过形成 N-C 键合成含氮有机化合物

摘要

Ñ含有机化合物的对生命至关重要。宝贵的实践合成ñ直接从含二氮的有机化合物（N ₂），而不是通过氨（NH ₃），是一种神圣-圣杯在化学和化学工业。这种转变的一个重要步骤是激活的 N ₂单元/配体的功能化以生成 NC 键。过渡金属介导的 N ₂通过在金属-二氮 [N ₂-M]配合物产生了多样化的配位模式，为理解N-C键形成机制奠定了基础。这篇综述总结了这些主要成就，并按参与 N-C的 [N ₂ -M] 配合物（端对、侧对、端对侧等）的协调模式进行了组织。[N ₂ -M]配合物与碳基底物的反应类型（N-烷基化、N-酰化、环加成、插入等）。此外，还简要介绍了通过不明确的中间体从 N ₂一锅法合成有机化合物的早期工作。虽然几乎所有的N的合成迄今为止文献中通过直接转化 N _{2 的}含 有机化合物在均相化学计量热化学反应系统中实现并在此详细讨论，零星报道的涉及光化学、电化学、非均相热催化反应的合成（如果有的话）也是提及。本文旨在为读者提供所述状态的最先进和特别在N直接催化和有效转化未来研究的观点进行了深入的理解₂到Ñ温和的条件下含有机化合物，并激发更多为应对这一长期存在的重大科学挑战而进行的研究工作。