Electronic Structure Calculations: Dinitrogen Reduction in Nitrogenase and Synthetic Model Systems

Abstract

Theoretical studies on the binding and reduction of dinitrogen and alternative substrates at the iron‐molybdenum cofactor (FeMoco) of nitrogenase are reviewed. Before considering the enzymatic pathways, the available mechanistic scenarios for N 2 reduction in small‐molecule model systems are discussed. These systems are divided into those involving an end‐on terminal (Sections 2.1 and 2.2) and those involving a bridging coordination of N 2 (Section 2.3). For the enzyme, calculations of Noodleman et al ., Nørskov et al ., Blöchl et al ., Dance, and others are reviewed and compared to each other. Conclusions are drawn with respect to the most probable scenario of N 2 reduction at the FeMoco and the open mechanistic questions in this research area.