Zwei-und dreikernige Fluorooxoanionen des Vanadins. Kristallstrukturen von Cs(NMe₄)[V₂O₂F₈(H₂O)] und (Na,K)(NMe₄)₂[V₃O₃F₁2] / Di- and Trinuclear Fluorooxoanions of Vanadium. Crystal Structures of Cs(NMe₄)[VO₂F₈(H₂O)] and (Na,K)(NMe₄)₂[V₃O₃F₁₂]

Abstract

F luorooxovanadates(V ), Crystal Structure From aqueous HF solutions the follow ing fluorooxo com plexes have been crystallized and characterized: A I(N M e4)2[V 3 0 3F 12] (1), A 1 = N a. K; K2(N M e4)[V 20 2Fc,] • H20 (2); C s(N M e4)[V 20 2F8(H :0 ) ] (3) and N M e4[V O F4] (4). The structures of 1 and 3 have been deter mined. Crystal data: lc, hexagonal, space group P 6ym . a -1695.0(9), c = 1248.1(5) pm. Z = 6: 1803 reflections. R = 0.045. 3, orthorhom bic. space group Pnma, a = 2152.8(7), b = 751.5(2), c = 850.7(2) pm, Z = 4; 1379 reflections, R = 0.030. 1 contains a trimeric, cyclic anion with asymmetrical ly bonded w-fluoroligands and terminal V = 0 groups in the same plane; the anion o f 3 is a fluorobridged dimer with unequally coordinated vanadium atom s with terminal V = 0 groups. The preparation o f these com pounds establishes the presence o f V 0 F 4(H :0 ) species in aqueous solutions.

Structural chemistry of organically-templated metal fluorides

“…which contains an unsymmetrical anionic dimer of fused VOF 5 and VOF 4 (H 2 O) octahedra. 27 Several other cations give similar dimers: Mo VI , Ta V , W VI , W IV . Infinite inorganic architectures can also be obtained when coordination complexes link the dimeric units (see Section 3).…”

Reactivity of VOF3 with N-Heterocyclic Carbene and Imidazolium Fluoride: Analysis of Ligand–VOF3 Bonding with Evidence of a Minute π Back-Donation of Fluoride

“…4 Reactions of VOF 3 with nitrogen and oxygen donor ligands usually lead to the formation of neutral VOF 3 complexes, while use of phosphorus or arsenic ligands leads to the formation of varying amounts of products including [VOF 3 (OEPh 3 ) 2 ] (E = P or As) and compounds with [VOF 4 ] − anion according to NMR spectroscopy. 5 Reactions of VOF 3 with fluoride donors lead to the formation of different anionic species including [VO-F 5 ] 2− , 6−9 [V 2 O 2 F 8 ] 2− , 10 [V 2 O 2 F 9 ] 3− , 11 and [V 3 O 3 F 12 ] 3− . 11 The most common method for the preparation of such species is nowadays solvothermal synthesis; however, reduction of vanadium(V) to vanadium(IV) or even vanadium(III) during such procedures is quite common.…”

“…5 Reactions of VOF 3 with fluoride donors lead to the formation of different anionic species including [VO-F 5 ] 2− , 6−9 [V 2 O 2 F 8 ] 2− , 10 [V 2 O 2 F 9 ] 3− , 11 and [V 3 O 3 F 12 ] 3− . 11 The most common method for the preparation of such species is nowadays solvothermal synthesis; however, reduction of vanadium(V) to vanadium(IV) or even vanadium(III) during such procedures is quite common. 12−14 First of the prepared vanadium(V) oxide fluorides containing [VOF 4 ] − anion was reported for the CsVOF 4 .…”

Solvothermal indium fluoride chemistry: Syntheses and crystal structures of K5In3F14, β-(NH4)3InF6 and [NH4]3[C6H21N4]2[In4F21]

“…6, there is a close matching between the 3-fold axes of the [In 3 F 15 ] 6 À and [C 6 H 21 N 4 ] 2 + units and it is therefore tempting to conclude that the formation of the trimeric In-F unit is templated by the organic cation. Trimeric units are rather rare in metal fluoride chemistry; indeed this appears to be the first crystallised example of an isolated [M 3 F 15 ] unit, although related oxyfluoride trimers exist in MoOF 4 , TcOF 4[29] and K[C 4 H 12 N][V 3 O 3 F 12 ][30]. Although Na + was present in the reaction mixture it was not incorporated into the product.…”