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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)(PtPr3)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. [ABSTRACT FROM AUTHOR]

Treatment of [Et4N]2[WSe4] with a 1:1 mixture of AgNO3 and PCy3 (Cy = cyclohexyl) in the absence of iodide afforded a linear trinuclear compound [(μ-WSe4)(AgPCy3)2] (1). A similar reaction in the presence of iodide gave rise to the isolation of the cubanelike compound [(μ3-WSe4)Ag3(PCy3)3(μ3-I)] (2). Treatment of [Et4N]2[WSe4] with Agi in the presence of bidentate phosphine ligands bis(diphenylphosphino)amine (dppa) and bis(diphenylphosphino)-methane (dppm) afforded the tetranuclear compounds [(μ3-WSe4)Ag3(μ-l)(μ-dppa)2] (3) and [(μ3-WSe4)Ag3(μ3-I)-(μ-dppm)2] (4), respectively, which exhibit an open butterfly configuration. A novel hexanuclear cluster compound [(μ3-WSe4)2Ag4(μ-dppm)3] (5) was obtained from interaction of [Et4N]2[WSe4] with AgNO3 and dppm in the absence of iodide source. The above cluster compounds are electrically neutral and air-stable in both solution and the solid state and have been characterized by electronic, infrared, mass, and NMR spectroscopies. The solid-state structures of five cluster compounds have been established by X-ray crystallography. The nonlinear optical properties of compounds 4 and 5 were examined by z-scan techniques with 7 ns pulses at 532 nm. The optical limiting effects of compounds 1, 2, 4, and 5 were determined and compared with related argentoselenometallic compounds. [ABSTRACT FROM AUTHOR]