Synthesis and Reactivity of Triiron Complexes Containing Selenide and Diselenide Bridging Ligands: X-ray Structure of [Cp*3Fe3(μ2-Se)(μ3-Se2)2](PF6)(Cp*=η5-C5Me5)

Abstract Reaction of Cp*2Fe2(CO)4 with red selenium (Se8) afforded an unexpected selenium-rich triiron complex Cp*3Fe3Se5(1). Air oxidation of 1 in the presence of NH4PF6 gave the monocationic complex [Cp*3Fe3Se5] (PF6) (2). An X-ray crystal structure analysis of 2 revealed that an Fe3Se5 core consists of three iron atoms, one μ2-selenide ligand, and two μ3-diselenide ligands with a side-on manner. Reactions of 2 with some simple reagents were also examined.