title: Chemical activity of the nitrogenase FeMo cofactor with a central nitrogen ligand: density functional study.
abstract: We investigate the chemical consequences of a central ligand in the nitrogenase FeMo cofactor using density functional calculations. Several studies have shown that the central ligand most probably is a nitrogen atom, but the consequences for the chemical reactivity of the cofactor are unknown. We investigate several possible routes for insertion of the central nitrogen ligand and conclude that all routes involve barriers and intermediate states, which are inaccessible at ambient conditions. On this basis we suggest that the central nitrogen ligand is present at all times during the reaction. Furthermore, we investigate how the FeMoco with the central ligand can interact with N(2) and reduce it.
authors.affiliation: Center for Atomic-scale Materials Physics, Department of Physics, Building 307, Technical University of Denmark, DK-2800 Lyngby, Denmark.
authors.forename: Berit
authors.initials: B
authors.lastname: Hinnemann
authors.forename: Jens K
authors.initials: JK
authors.lastname: Nørskov
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D008024:Ligands; D008956:Models, Chemical; D008958:Models, Molecular; D008983:Molybdoferredoxin / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D008024:Ligands; D008983:Molybdoferredoxin; D000641:Ammonia; D009584:Nitrogen