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(DDP)6([μ4-S or O)]

A high purity synthesis of chloride-{Cu-8[S-2((OPr)-Pr-i)(2)](6)(mu(8)-Cl)}[PF6] (1) and bromide-{Cu-8[S-2((OPr)-Pr-i)(2)](6)(mu(8)-Br)}[PF6] (2) centered Cu-8 cubic clusters has been achieved through the reaction of [Cu(CH3CN)(4)]PF6 and NH4[S2P((OPr)-Pr-i)(2)] in the presence of [BzEt(3)N]X (X = Cl or Br) in THF upon addition of an appropriate oxidant. The nearly perfect Cu-8 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 Cu-8 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) Angstrom (1 and 2, respectively). The average Cu-S distance is 2.282(2) Angstrom in 1 and 2.295(3) Angstrom 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, [Zn-4(DDP)(6)(mu(4)-S or O)] which have the classic "basic" beryllium acetate geometry. The structural relationship to the hexanuclear clusters Cu-6[S-2(OR)(2)](6), R = ethyl or n-butyl, also are described. (C) 2004 Elsevier B.V. All rights reserved.