Synthesis and structure of two ionic copper indium selenolate cluster complexes [As(C6H5)4]2[Cu 6In4(SeC6H5)16Cl 4] and [As(C6H5)4]-[Cu 7In4(SeC6H5)20]

Abstract

The reaction of PhSeSiMe3, CuCl, InCl3, and Ph 4AsCl in CH2Cl2 results in crystals of the structurally closely related, ionic clusters (AsPh4) 2[Cu6In4Cl4(SePh)16] and (AsPh4)-[Cu7In4(SePh)20], with product ratios dependent on the initial PhSeSiMe3 concentration. Both molecules display a fused four-adamantoid structure related to the solid-state structure of CuInSe2. Since the crystallographic analysis for [Cu7In4-(SePh)20]- remained ambiguous with respect to the assignment of one of the copper atoms, we performed a high-resolution mass spectrometric analysis as well as DFT computations to address this problem. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.