Electrochemical behaviour of [Fe6M2S8-(SR),I3-(M = M o br W) and the roles of molybdenum and tungsten in nit rogenasesREPORTS of the isolation and properties 2 9 3 of the Fe-Mo cofactor of nitrogenase and the structural inferences obtained from extended X-ray absorption fine structure (EXAFS) studies of this molybdenum centre have prompted much synthetic work in pursuit of this entity. Currently, Fe,MoS, cubane-like cluster compounds represent the best synthetic analogues for the molybdenum centre of nitrogenase. In these complexes, Mo is six-co-ordinate where Fe is four-co-ordinate and, in the majority of complexes so far reported, the three ligands attached to the Mo and external to the cube bridge to an identical molybdenum centre. Corresponding systems containing Fe,WS, clusters have also been prepared. Comparisons between these Fe,RloS, and Fe,WS, systems are of interest, not least because W, although incorporated into the FeMo protein of nitrogenase in place of Mo, apparently does not lead to a functional enzyme.The crystal structures of [NEt,],[Fe,MO,S,(SEt),] and [NEt4]3[Fe6W2S8(SEt)9] show that, if Fe,MoS, clusters are valid structural analogues for the immediate molybdenum environment in nitrogenase, there are no steric impediments to W being incorporated into such a site.8 Compounds containing Fe,MS, (M = Mo or W) cubane-