Metalloenzyme cofactors mediate multi-electron activation of highly unactivated substrates.  Nitrogenase features a polynuclear cofactor, which catalyzes the biological conversion of dinitrogen to ammonia.  While interest in synthetic metal clusters and their ability to mediate multi-electron chemistry has grown, clusters that feature high spin, coordinatively unsaturated metal faces by which investigation of substrate binding and activation can be conducted is currently lacking in the literature.  Our approach entails the synthesis of a family of hexadentate ligand scaffolds that can support a tri-metallic core and allow systematic structural-activity analysis through control of the steric and electronic environment of the cluster.  These complexes could serve as functional surrogates for polynuclear reaction sites found in metalloenzyme cofactors.  We recently reported the synthesis of a triiron cluster tbsLFe3(THF) and demonstrated its ability to mediate multielectron reaction chemistry.  Further reactivity of cluster tbsLFe3(THF) will be discussed in the context of nitrogenase-type reactivity.

Trinuclear iron complexes for cooperative small molecule activation

245th National Meeting (2013)

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