Synthesis and characterization of polynuclear half-sandwich lanthanoid complexes [Na(THF) 6] 2[Cp t6Sm 6Se 13] and [Li(THF) 4] 2[Cp 6Nd 6Se 13

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The half-sandwich tert-butyl cyclopentadienyl lanthanoid complexes {[Cp t Ln(THF)] 2(μ 2-Cl) 2(μ 3-Cl) 3Na(THF)} n [Cp t =η 5- t BuC 5H 4; Ln=Nd ( 1a), Sm ( 1b), Gd ( 1c), Yb ( 1d)] are prepared by the reaction of anhydrous lanthanoid trichloride, LnCl 3, with NaCp t in THF solution. Complex 1b reacts with Na 2Se 5 to give hexanuclear samarium polyselenide complexes [Na(THF) 6] 2[Cp t 6Sm 6(μ 6-Se)(μ-Se 2) 6] ( 2). An analogous cyclopentadienyl neodymium polyselenide complex [Li(THF) 4] 2[Cp 6Nd 6(μ 6-Se)(μ-Se 2) 6] ( 3) is synthesized by the reaction of [CpNdCl 2·2LiCl·5THF] with Na 2Se 5 in THF solution. The molecular structures of 1a and 2 were determined by X-ray crystal structure analysis. Complex 2 contains an interstitial selenium atom which is coordinated with six samarium atoms.