CHAPTER 6: Nitrogen Fixation in Nitrogenase and Related Small-Molecule Models: Results of DFT Calculations

Theoretical studies on the binding and reduction of dinitrogen at the iron–molybdenum cofactor (FeMoco) of nitrogenase are reviewed. Before considering the enzyme, mechanistic scenarios for the protonation and reduction of N₂ in related small-molecule models are discussed. Particular emphasis is laid on describing DFT calculations of catalytic systems. With respect to corresponding calculations on the enzyme, theoretical treatments of the FeMoco and of dinitrogen reduction at this cluster published by Noodleman, Nørskov, Blöchl, Dance and others are reviewed and compared with the available experimental data.