Ferrocenyldiselenolate-Stabilized Copper−Selenium Clusters

The silylated ferrocenyl selenium reagent 1,1‘-Fe(η5-C5H4SeSiMe3)2 has been used for the high yield formation of
the phosphine-ligated copper complexes Cu2(fcSe2)(PiPr3)2 (1) and Cu4(fcSe2)2(PnPr3)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(Se2fc)4(PnPr3)10] (3).
Partial substitution of the PnPr3 ligand shell in 3 with the phosphinothiol Ph2P(CH2)3SH leads to an expansion of
the framework and the high yield formation of the crystallographically characterized cluster Cu36(fcSe2)6Se12(PnPr3)10(Ph2P(CH2)3SH)2 (5), which contains surface alkylthiol groups on a copper−selenium core.