Direct transformation of dinitrogen: synthesis of <i>N</i>-containing organic compounds via N−C bond formation

Abstract

<i>N</i>-containing organic compounds are of vital importance to lives. Practical synthesis of valuable <i>N</i>-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 (<i>N</i>-alkylation, <i>N</i>-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 <i>N</i>-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 <i>N</i>-containing organic compounds under mild conditions, and to stimulate more research efforts to tackle this long-standing and grand scientific challenge.