Direct Incorporation of Dinitrogen into an Aliphatic C–H Bond

Abstract

The activation of dinitrogen (N 2 ) and direct incorporation of its N atom into C−H bonds to create aliphatic C−N compounds remains unresolved. Incompatible conditions between dinitrogen reduction and C−H functionalization make this process extremely challenging. Herein, we report the first example of dinitrogen insertion into an aliphatic Csp 3 −H bond on the ligand scaffold of a 1,3-propane-bridged [N 2 N] 2− -type dititanium complex. Mechanistic investigations on the behaviors of dinuclear and mononuclear Ti complexes indicated the intramolecular synergistic effect of two Ti centers at a C−N bond-forming step. Computational studies revealed the critical isomerization between the inactive side-on N 2 complex and the active nitridyl complex, which is responsible for the Csp 3 −H amination. This strategy maps an efficient route toward the future synthesis of aliphatic amines directly from N 2 .

Benchmark Study of Density Functional Theory Methods in Geometry Optimization of Transition Metal–Dinitrogen Complexes

“…The design of novel [N 2 N] 2– -type dinuclear and trinuclear Ti–N 2 complexes by Shi and co-workers highlights the ongoing efforts to develop new catalysts for nitrogen fixation. Unprecedented N 2 fixation and insertion into aliphatic hydrocarbon in one pot via a bimetallic system were first discovered and reported in 2023 …”

“…Unprecedented N 2 fixation and insertion into aliphatic hydrocarbon in one pot via a bimetallic system were first discovered and reported in 2023. 30 With the vigorous development of the coordination chemistry of this simple molecule, dinitrogen complexes exhibit a variety of binding modes. It is interesting to know that dinitrogen can be fixed on the single metal site of transition metal complexes through end-on or side-on configuration and that the monometallic end-on coordination mode is more common than the monometallic side-on coordination mode (Figure 1, left).…”

Single Atom Catalysts for Photoelectrochemical Water Splitting

“…Research conducted by techno‐economic modeling has indicated that it is imperative to develop PEC water electrolysis cells with an efficiency higher than 10 % and stability of more than 10 years to compete with conventional methane steam reforming [37–42] . Since the PEC performances of photoelectrodes are influenced by the electron‐hole pair generation, separation, transport, and surface reaction, the loss of photo‐induced charge carriers in these processes should be suppressed [43–46] . In this respect, it is required to develop highly active catalysts, charge transport layers, as well as passivation layers.…”

Systematic degradation analysis in renewable energy-powered proton exchange membrane water electrolysis

“…3 Solar power, utilized for electrochemical or photoelectrochemical water splitting, is the largest source of renewable energy by far and has attracted considerable research interest. [4][5][6][7] Therefore, renewable energy-powered water electrolysis, so-called green hydrogen production, should be the focus of the next decade.…”