Rectangular tetranuclear silver(I) and μ8-selenide-centered octanuclear copper(I) complexes containing bis(diphenylphosphino)amide ligands

Interaction of Ag(CF3CO2) with bis(diphenylphosphino)amide (dppa) in THF gave a tetranuclear Ag4-coplanar silver(I) complex [Ag4(μ-dppa)2(μ4-O2PPh2)2(μ-CF3CO2)2] (1). The trinuclear trigonal-bipyramid copper(I) complex [Cu3(μ3-Cl)2(μ-dppa)3][CuCl2] (2) was obtained from the reaction of [CuCl] powder with bis(diphenylphosphino)amide (dppa) in THF. Treatment of 2 with (Me3Si)2Se in THF afforded a μ8-selenide-centered octanuclear copper(I) complex [Cu8(μ8-Se)(μ4-Se)(μ4-SeH)3(μ-dppa)4][(Ph2PO)2N] (3). The structures of 1–3 were determined by single-crystal X-ray diffraction analyses. Complex 1 comprises a rectangular Ag4 array with each edge bridged with a pair of μ-dppa, μ4-O2PPh2 and μ-CF3CO2 ligands that are approximately perpendicular to each other. Complex 2 contains a trigonal-bipyramid [Cu3(μ3-Cl)2]+ core surrounded by three μ-dppa ligands. The cationic complex in 3 consists of four [Cu2(μ-dppa)] fragments side-capped by one μ4-Se and three μ4-SeH ligands and center-connected by a μ8-Se atom.