Die Kristallstrukturen von PPh₄[WOCl₄], (PPh₄)₂[WOCl₅] · ₂CH₂CI₂ und (PPh₄)₂[ReOCl₅] · ₂CH₂Cl₂ / The Crystal Structures of PPh₄[WOCl₄], (PPh₄)₂[WOCl₅] · ₂CH₂CI₂ and (PPh₄)₂[ReOCl₅] · ₂CH₂Cl₂

Abstract

Both tungsten compounds are formed by reaction of water and oxygen with the acetylene complex PPh 4 [WCl 5 (Ph - C ≡ C - C (Br) = C(Br) -Ph)] in CH 2 Cl 2 solutions, and in the presence of PPh 4 Cl. PPh 4 [WOCl 4 ] crystallizes in the tetragonal space group P4/n, with two formula units in the unit cell of dimensions a = b = 1269, c = 760 pm at -110 °C (1416 observed in dependent reflexions, R = 0 .054). The [WOCl 4 ] ⊖ ion forms a tetragonal pyramid with the oxygen ligand in axial position and a tungsten -oxygen distance of 168 pm. (PPh 4 ) 2 [WOCl 5 · 2 CH 2 Cl 2 crystallizes in the tricline space group P 1̄, with one formula unit per unit cell with a = 1011, b = 1113, c = 1240 pm, α = 70.3°, β = 79.4°, γ = 80.9° at - 110 °C (3781 observed in dependent reflexions, R = 0 .087). The structure contains [WOCl 5 ] 2 ⊖ an ions where the oxygen atom and the chlorine atom in transposition are disordered. (PPh 4 ) 2 [ReOCl 5 ] · 2CH 2 Cl 2 is formed by the reaction of ReCl 5 with PPh 4 Cl in the presence of water. The compound is isotypic with the corresponding tungsten complex (space group P 1̄, Z = 1, a = 1006, b = 1109, c = 1239 pm , α = 7 0.5°, β = 79.6°, γ = 80.9° at -110 °C; 5436 observed in dependent reflexions R = 0 .050).