Synthesis and Characterisation of [XeF₅]₃[Ti₄F₁₉] Containing a Discrete [Ti₄F₁₉]^3– Anion

Abstract

The complex [XeF5]3[Ti4F19] was prepared by reaction of XeF2, TiF4 and UV‐irradiated elemental fluorine in anhydrous hydrogen fluoride as the solvent. The crystal structure of [XeF5]3[Ti4F19] consists of [XeF5]+ cations and discrete [Ti4F19]3– anions. The [XeF5] units have usual slightly distorted pseudo‐octahedral symmetry. Contrary to the previously reported [Ti4F18]2– anion, where each TiF6 octahedron shares three apexes with three other octahedra, in [Ti4F19]3–, only two μ3‐[TiF6] octahedra share three apexes with three other [TiF6] units. Each of the remaining two μ2‐[TiF6] octahedra shares only two vertices with two of the above‐mentioned μ3‐[TiF6] moieties. The Raman spectrum of [XeF5]3[Ti4F19] is in agreement with the presence of [XeF5]+ cations and [Ti4F19]3– anions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV)

“…In the XeF 6 /TiF 4 system, it has been already shown how previously formulated XeF 6 · TiF 4 and XeF 6 · 2TiF 4 are more correctly described as [XeF 5 ][TiF 5 ] and [XeF 5 ] 5 [Ti 10 F 45 ], respectively . Similarly, 3XeF 6 · 4TiF 4 and XeF 6 · 3TiF 4 correspond to [XeF 5 ] 3 [Ti 4 F 19 ] and [XeF 5 ][Ti 3 F 13 ], respectively , . The anionic parts in the crystal structures of [XeF 5 ][TiF 5 ] and [XeF 5 ][Ti 3 F 13 ] are polymeric; that is, there are ([TiF 5 ] – ) ∞ infinite chains for the former and ([Ti 3 F 13 ] – ) ∞ infinite columns for the latter.…”

“…[5] Similarly, 3XeF 6 ·4TiF 4 F 13 ], respectively. [5,6] 10 F 45 ] 5anion is the largest known example of a discrete oligomeric perfluorometallate anion with the highest rate of association of [M n+ F 6 ] n-6 octahedra.…”

[XeF5]+/Metal and [XeF5]+/Non‐Metal Mixed‐Cation Salts of Hexafluoridoantimonate(V)

“…It was observed fairly quickly that XeF 6 is a very good fluoride ion donor forming [XeF 5 ] + or [Xe 2 F 11 ] + salts. None of the compounds reported so far contain any additional cations and studies on crystal structure that we are aware of have stated that they are simple [Xe 2 F 11 ] + or [XeF 5 ] + salts of various fluorido anions, with square planar [MF 4 ] – (M = Ag, Au),5,6 octahedral [MF 6 ] – (M = As, V, Nb, Ru, Au, Pt),5,6 polymeric [MF 5 ] – (M = Cr, Ge),5,6 octahedral [MF 6 ] 2– (M = Ni, Pd),5,6 or oligomeric [Ti 4 F 19 ] 3– geometries 7. Exceptions are XeF 2 · n (XeF 5 AsF 6 ) ( n = 2, 1, 0.5),8 XeF 2 · (XeF 5 RuF 6 ),9 and (XeF 5 CrF 5 ) · XeF 4 10 where additional ligands (XeF 2 , XeF 4 ) are present and the recently reported [XeF 5 ] + and [Xe 2 F 11 ] + salts with [OsO 3 F 3 ] and [μ‐F(OsO 3 F 2 ) 2 ] anions 11…”

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF5]+ and [Xe2F11]+ Salts of the [CrVIOF5]−, [CrVOF5]2−, [CrV2O2F8]2−, and [CrIVF6]2− Anions

“…The bond lengths, bond angles, and Xe‐ ‐ ‐F contact distances of [XeF 5 ] + and [Xe 2 F 11 ] + in all six salts (Tables S2–S6, Supporting Information) are comparable to those of [Xe 2 F 11 ][AuF 6 ], [Xe 2 F 11 ] 2 [NiF 6 ], [XeF 5 ] 3 [Ti 4 F 19 ], [XeF 5 ][OsO 3 F 3 ], [Xe 2 F 11 ][OsO 3 F 3 ], and [XeF 5 ][μ‐F(OsO 3 F 2 ) 2 ] …”

“…. [53] [Xe 2 F 11 ] 2 [NiF 6 ], [55] [XeF 5 ] 3 [Ti 4 F 19 ], [56] [XeF 5 ][OsO 3 F 3 ], [51] [Xe 2 F 11 ] [OsO 3 F 3 ], [51] and [XeF 5 ][m-F(OsO 3 F 2 ) 2 ]. [51] The [XeF 5 ] + cation geometry may be described in terms of an AX 5 EV SEPR arrangement of five bond pairs (X) and av alence electron lone pair (E) aroundX e( A) which resultsi ni ts square-pyramidal geometry.…”