The Role of Mo Atoms in Nitrogen Fixation: Balancing Substrate Reduction and Dihydrogen Production

Abstract

The core issue: Cofactors in nitrogenases transform dinitrogen into ammonia, and protons into dihydrogen (see scheme). Studies on cuboidal {Fe4S4}2+ and {MoFe3S4}3+ clusters show that Mo clusters are protonated more slowly, but have a higher affinity for binding substrates, than Mo-free clusters. These reactivities explain why the Mo-based nitrogenase is the most efficient at fixing dinitrogen rather than producing dihydrogen. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2003/z50090_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.