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

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 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. Besides, 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 in-depth understanding of the state-of-the-arts 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 longstanding and grand scientific challenge.

Electrocatalytic Refinery for Sustainable Production of Fuels and Chemicals

“…N-containing chemicals,such as urea, amides,amines,and nitriles,a re of widespread importance for the production of bulk chemicals,synthetic intermediates,fertilizers,agrochemicals,a nd pharmaceuticals. [81][82][83] Currently,t he synthesis of these molecules is all dominated by the thermocatalytic transformation of NH 3 precursors under harsh conditions, which consumes more than half of the global ammonia production. [84] In contrast, electrocatalytic C-N coupling reactions are highly advantageous because they can directly convert abundant feedstocks (e.g., N 2 ,CH 4 )and even wastes (e.g.,C O 2 ,N O 3 À )i nto targeted complex molecules under ambient conditions.…”

Uranium(III)–Phosphorus(III) Synergistic Activation of White Phosphorus and Arsenic

“…Metal-mediated small-molecule activation is a burgeoning field of chemistry that produces useful chemicals from inexpensive feedstocks, such as N 2 . [1][2][3][4] This chemistry has been extensively investigated for the d-block transition metals, but the corresponding f-block chemistry is still in its infancy. 5 Molecular uranium complexes exhibit the attractive ability to activate small molecules.…”

The impact of alkali and alkaline earth metals on green ammonia synthesis

“…The importance of AM can be extended to N 2 functionalization beyond ammonia, especially for the synthesis of valuable N-containing organic compounds. 101 Typically, the presence of AM can effectively tune the reactivity of coordinated N 2 toward various N-C, N-Si, and N-B bond formation reactions under appropriate conditions. 45,101 Moreover, a catalytic process for synthesizing N-containing chemicals, such as diarylamines, triarylamines, and N-heterocycles, from N 2 has been developed by Shi et al very recently, where Li 3 N, generated in situ by reacting Li with N 2 , supplies reactive N species to react with organohalides for constructing C-N bonds.…”

“…101 Typically, the presence of AM can effectively tune the reactivity of coordinated N 2 toward various N-C, N-Si, and N-B bond formation reactions under appropriate conditions. 45,101 Moreover, a catalytic process for synthesizing N-containing chemicals, such as diarylamines, triarylamines, and N-heterocycles, from N 2 has been developed by Shi et al very recently, where Li 3 N, generated in situ by reacting Li with N 2 , supplies reactive N species to react with organohalides for constructing C-N bonds. 102 We believe that the above discussions/understandings of AM in ammonia synthesis would stimulate ideas and research efforts on N 2 functionalization as well.…”