Development of Coordinatively Unsaturated Iron Complexes Having Organosilyl Ligands for Activation of Molecular Dinitrogen

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Dinitrogen fixation mediated by homogeneous transition metal complexes is one of the most important process from both academic and industrial point of view. In this research, molecular dinitrogen was revealed to be captured by iron complex bearing the chelating organosilyl ligand. Namely, reaction of 2 equivalent of 1, 2-bis(dimethylsilyl) benzene with[ Fe(mesityl) 2] 2 in aromatic solvent under nitrogen atmosphere afforded the dinuclear bis(organosilyl) iron complexes,[(η6-arene) Fe(Me2SiC6H4SiMe2)] 2(μ-η1 :η1-N2), that have a end-on bound bridging dinitrogen ligand. The dinitrogen unit easily dissociated from the Fe center to generate the mononuclear(η6-arene) Fe(II)(Si) 2L or(η6-arene) Fe(IV)(Si) 2H2 complexes by the reactions with CO, PPh3, and H2.