Synthetic Analogues of Nitrogenase Metallocofactors: Challenges and Developments

Abstract

Nitrogenase is the only known biological system capable of reducing N₂ to NH₃ , which is a critical component of bioavailable nitrogen fixation. Since the discovery of discrete iron-sulfur metalloclusters within the nitrogenase MoFe protein, synthetic inorganic chemists have sought to reproduce the structural features of these clusters in order to understand how they facilitate the binding, activation and hydrogenation of N₂ . Through the decades following the initial identification of these clusters, significant progress has been made to synthetically replicate certain compositional and functional aspects of the biogenic clusters. Although much work remains to generate synthetic iron-sulfur clusters that can reduce N₂ to NH₃ , the insights borne from past and recent developments are discussed in this concept article.

Keywords: M-cluster; P-cluster; biomimetic synthesis; cofactors; nitrogenase.