Synthesis, structure and reactions of triply selenolate-bridged diiron complex [Cp*Fe(μ-SeMe)3FeCp*]

Two new iron–selenolate complexes [Cp*Fe(μ-SeMe)3FeCp*] (Cp* = η5-C5Me5) (1) and [Cp*Fe(μ-SeMe)3FeCp*][FeCl3] (2) were prepared by the oxidative addition reaction of MeSeSeMe with [Cp*FeCl]2 in 25% and 20% yields, respectively. In refluxing toluene, the methyl groups in the selenolate ligands of complex 1 were removed, affording a cubane cluster [Cp*4Fe4Se4] (3) in 50% yield. Complex 1 was oxidized by HBF4 to give [Cp*Fe(μ-SeMe)3FeCp*][BF4] (4), and the reverse reduction reaction occurred in the presence of CoCp2.

Graphical abstractPresented here is the syntheses of [Cp*Fe(μ-SeMe)3FeCp*] and [Cp*Fe(μ-SeMe)3FeCp*][FeCl3] by the oxidative addition reaction of MeSeSeMe with [Cp*FeCl]2. The conversion of [Cp*Fe(μ-SeMe)3FeCp*] into [Cp*4Fe4Se4] and [Cp*Fe(μ-SeMe)3FeCp*]+ were also explored.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Four new selenolate-bridged multi-iron clusters with Cp* as ligand were prepared. ► [Cp*Fe(μ-SeMe)3FeCp*] was converted into a cubane-type complex in heating toluene. ► [Cp*Fe(μ-SeMe)3FeCp*] and [Cp*Fe(μ-SeMe)3FeCp*]+ are interconvertible.