Ferrocenyldiselenolate-stabilized copper-selenium clusters

The silylated ferrocenyl selenium reagent 1,1'-Fe(eta(5)-C5H4SeSiMe3)(2) has been used for the high yield formation of the phosphine-ligated copper complexes Cu-2(fcSe(2))(PiPr(3))(2) (1) and Cu-4(fcSe(2))(2)(PnPr(3))(4) (2) from solublilized CuOAc, as determined by single-crystal X-ray diffraction. The incorporation of a source of Se2- into the reaction scheme with the reagent Se(SiMe3)(2) yields the mixed selenide/ferrocenyldiselenolate cluster [Cu20Se6(Se(2)fc)(4)(PnPr(3))(10)] (3). Partial substitution of the PnPr(3) ligand shell in 3 with the phosphinothiol Ph2P(CH2)(3)SH leads to an expansion of the framework and the high yield formation of the crystallographically characterized cluster Cu-36(fcSe(2))(6)Se-12(PnPr(3))(10)(Ph2P(CH2)(3)SH)(2) (5), which contains surface alkylthiol groups on a copper-selenium core.