Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Abstract

Dinitrogen (N 2 ) is the most abundant gas in the Earth’s atmosphere, but its inertness hinders its use as a nitrogen source in the biosphere and in industry. Efficient catalysts are hence required to overcome the high kinetic barriers associated to N 2 transformation. In that respect, molecular complexes have demonstrated strong potential to mediate N 2 functionalization reactions under mild conditions while providing a straightforward understanding of the reaction mechanisms. This review emphasizes the strategies for N 2 reduction and functionalization using molecular transition metal and actinide complexes according to their proposed reaction mechanisms, distinguishing complexes inducing cleavage of the N≡N bond before (dissociative mechanism) or concomitantly with functionalization (associative mechanism). We present here the main examples of stoichiometric and catalytic N 2 functionalization reactions following these strategies. © 2020 Wiley‐VCH GmbH.