Cluster self-assembly of centered cubes of copper(I) with dialkyldithiophosphate ligands. X-ray structures of [Cu8(DDP)6(μ8-X)]PF6 (DDP = S2P(OiPr)2; X = Cl or Br) and their relationship to oxide and sulfide centered zinc(II) dialkyldithiophosphates, [Zn4

A high purity synthesis of chloride-{Cu8[S2P(OiPr)2]6(μ8-Cl)}[PF6] (1) and bromide-{Cu8[S2P(OiPr)2]6(μ8-Br)}[PF6] (2) centered Cu8 cubic clusters has been achieved through the reaction of [Cu(CH3CN)4]PF6 and NH4[S2P(OiPr)2] in the presence of [BzEt3N]X (X = Cl or Br) in THF upon addition of an appropriate oxidant. The nearly perfect Cu8 cube encapsulates the closed shell ions Cl− or Br−. The six diisopropyl dithiophosphate ligands bridge across each face of the Cu8 cube to form a nearly regular icosahedron of S atoms about the centered Cu8 cube. The eight Cu(I) atoms are located at the cube corners with an average Cu–Cu distance of 3.113(2) and 3.167(1) Å (1 and 2, respectively). The average Cu–S distance is 2.282(2) Å in 1 and 2.295(3) Å in 2. There appears to be a direct structural relationship between these centered cubal structures and the tetranuclear zinc(II) oxide and sulfide centered dialkyldithiophosphates, [Zn4(DDP)6(μ4-S or O)] which have the classic “basic” beryllium acetate geometry. The structural relationship to the hexanuclear clusters Cu6[S2P(OR)2]6, R = ethyl or n-butyl, also are described.