Rectangular tetranuclear silver(I) and μ 8-selenide-centered octanuclear copper(I) complexes containing bis(diphenylphosphino)amide ligands

Abstract

Interaction of Ag(CF 3CO 2) with bis(diphenylphosphino)amide (dppa) in THF gave a tetranuclear Ag 4-coplanar silver(I) complex [Ag 4(μ-dppa) 2(μ 4-O 2PPh 2) 2(μ-CF 3CO 2) 2] ( 1). The trinuclear trigonal-bipyramid copper(I) complex [Cu 3(μ 3-Cl) 2(μ-dppa) 3][CuCl 2] ( 2) was obtained from the reaction of [CuCl] powder with bis(diphenylphosphino)amide (dppa) in THF. Treatment of 2 with (Me 3Si) 2Se in THF afforded a μ 8-selenide-centered octanuclear copper(I) complex [Cu 8(μ 8-Se)(μ 4-Se)(μ 4-SeH) 3(μ-dppa) 4][(Ph 2PO) 2N] ( 3). The structures of 1– 3 were determined by single-crystal X-ray diffraction analyses. Complex 1 comprises a rectangular Ag 4 array with each edge bridged with a pair of μ-dppa, μ 4-O 2PPh 2 and μ-CF 3CO 2 ligands that are approximately perpendicular to each other. Complex 2 contains a trigonal-bipyramid [Cu 3(μ 3-Cl) 2] + core surrounded by three μ-dppa ligands. The cationic complex in 3 consists of four [Cu 2(μ-dppa)] fragments side-capped by one μ 4-Se and three μ 4-SeH ligands and center-connected by a μ 8-Se atom.