Molecular Mechanism for Nitrogen fixation: first steps

Schimpl, Johannes; Petrilli, Helena M.; Bloechl, Peter E.

Molecular Mechanism for Nitrogen fixation: first steps

Authors

Schimpl, Johannes

Petrilli, Helena M.

Bloechl, Peter E.

Description

N2 association to the FeMo-cofactor of nitrogenase, including the recently identified central N ligand, has been investigated using first-principles electronic structure calculations. The oxidation state of the resting state of the cofactor and its electronic structure has been identified. A single proton is added to the sulfur bridges following each electron transfer to the cofactor. During N2 association, the cofactor undergoes large rearrangements resulting in opening the central Fe-cage of the cofactor. N2 binds axially while the bond of the bridging SH group breaks. It is then able to insert between the two Fe sites in a bridged configuration.
5 pages 2 Figures