Reaction of Selenium with Bromine in the Presence of Methyltriphenylphosphonium Bromide: Syntheses and Crystal Structures of [PMePh3]2[Se2Br6] and [PMePh3]2[SeBr6(SeBr2)2

Abstract

AbstractThe brown crystals of [PMePh3]2[Se2Br6] (1) and red crystals of [PMePh3]2[SeBr6(SeBr2)2] (2) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of methyltriphenylphosphonium bromide. The crystal structures of 1 and 2 has been determined by the X‐ray methods and refined to R = 0.0373 for 2397 reflections and 0.0397 for 3417 reflections, respectively. The salt 1 crystallizes in the monoclinic space group P21/n with the cell dimensions a = 13.202(5) Å, b = 11.954(4) Å, c = 13.418(6) Å, β = 93.08(4)° (193(2)). The crystals of 2 are triclinic, space group $P{\bar 1}$ with the cell dimensions a = 10.266(3) Å, b = 11.311(3) Å, c = 11.619(2) Å, α = 108.87(2)°, β = 105.72(2)°, γ = 99.40(2)° (193(2) K). In the solid state structure of 1 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square planar SeBr4 units sharing a common edge through two μ‐bridging Br atoms. The terminal SeII–Br bonds are 2.3984(11) and 2.4273(11) Å, whereas the bridging μBr–SeII bonds are 2.7817(11) and 2.9081(12) Å. In the solid state the trinuclear [SeBr6(SeBr2)2]2− anion of 2 is centrosymmetric too and contains a nearly regular [SeBr6] octahedron where the four equatorial bromo ligands each have developed bonds to the SeII atoms of the SeBr2 molecules. The contacts between the bridging bromo and the SeII atoms of the SeBr2 molecules are 3.0603(15) and 3.1043(12) Å, and can be interpreted as bonds of the donor‐acceptor type with the bridging bromo ligands as donors and the SeBr2 molecules as acceptors. The SeIV–Br distances are in the range 2.5570(9)–2.5773(11) Å and the SeII–Br bond lengths in coordinated SeBr2 molecules – 2.3411(12) and 2.3421(10) Å.