Standard Article

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

  1. Felix Tuczek

Published Online: 15 SEP 2009

DOI: 10.1002/0470862106.ia623

Encyclopedia of Inorganic Chemistry

Encyclopedia of Inorganic Chemistry

How to Cite

Tuczek, F. 2009. Electronic Structure Calculations: Dinitrogen Reduction in Nitrogenase and Synthetic Model Systems. Encyclopedia of Inorganic Chemistry. .

Author Information

  1. Christian-Albrechts-Universität Kiel, Kiel, Germany

Publication History

  1. Published Online: 15 SEP 2009

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 N2 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 N2 (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 N2 reduction at the FeMoco and the open mechanistic questions in this research area.

Keywords:

  • nitrogen fixation;
  • nitrogenase;
  • dinitrogen complexes;
  • bioinorganic chemistry;
  • metalloproteins;
  • DFT (density functional theory)