Abstract
Nitrogen fixation, the six-electron/six-proton reduction of N(2), to give NH(3), is one of the most challenging and important chemical transformations. Notwithstanding the barriers associated with this reaction, significant progress has been made in developing molecular complexes that reduce N(2) into its bioavailable form, NH(3). This progress is driven by the dual aims of better understanding biological nitrogenases and improving upon industrial nitrogen fixation. In this review, we highlight both mechanistic understanding of nitrogen fixation that has been developed, as well as advances in yields, efficiencies, and rates that make molecular alternatives to nitrogen fixation increasingly appealing. We begin with a historical discussion of N(2) functionalization chemistry that traverses a timeline of events leading up to the discovery of the first bona fide molecular catalyst system and follow with a comprehensive overview of d-block compounds that have been targeted as catalysts up to and including 2019. We end with a summary of lessons learned from this significant research effort and last offer a discussion of key remaining challenges in the field.