Modeling of the molybdenum center in the nitrogenase FeMo-cofactor

The functional, structural and theoretical chemical approaches to specifically model the molybdenum center of the nitrogenase enzyme are reviewed. We show how dinitrogen can be reduced at monometallic centers and highlight attempts to develop a nitrogenase-relevant dinitrogen reduction chemistry at molybdenum-sulfur complexes and clusters. The theoretical work addressing the molybdenum issue is also reported together with models for nitrogenase function, some of them directly involving the molybdenum atom. (C) 2002 Elsevier Science B.V. All rights reserved.