Formation and Structural Diversity of Organo-Functionalized Tin-Silver Selenide Clusters.

When reacting the organic functionalized tin selenide clusters [(SnR1 )3 Se4 Cl] (A, R1 =CMe2 CH2 C(O)Me) or [(SnR1 )4 Se6 ] (B) with (SiMe3 )2 Se and [Ag(PPh3 )3 Cl] at -78 °C in CH2 Cl2 , a microcrystalline intermediate (compound 1) precipitates, which was investigated by magic angle spinning (MAS) NMR spectroscopy, powder X-ray diffraction (PXRD), energy dispersive X-ray (EDX) spectroscopy, and quantum chemistry calculations, to derive information about its composition and structure. Compound 1 re-dissolves under reorganization into the organo-functionalized Ag/Sn/Se cluster compound [Ag6 (μ6 -Se)(Ag8 Se12 ){(R1 Sn)2 Se2 }6 ] (2), or the mixed-valence cluster [(AgPPh3 )2 (SnII Cl)2 Se2 {(R1 SnIV )2 Se2 }2 ] (3), depending on the presence or the exclusion of daylight, respectively. The addition of N2 H4 ⋅H2 O to a solution of 1 yields selectively [Ag7 (μ7 -Se)(Ag7 Se12 ){(R2 Sn)2 Se2 }6 ] (4, R2 =CMe2 CH2 C(N2 H2 )Me), the Ag/Sn/Se core of which is isomeric to that of 2. 2-4 were characterized by X-ray diffraction. NMR spectroscopic studies on solutions of 1 indicate the co-existence of different species.