Die Interhalogenkationen [Br₂F₅]⁺ und [Br₃F₈]⁺

Abstract

Die bislang einzigen Polyhalogenkationen, in denen verbrückende Fluoratome vorliegen, wurden synthetisiert und charakterisiert. Das [Br2F5]+‐Kation enthält eine symmetrische [F2Br‐μ‐F‐BrF2]‐Brücke, das [Br3F8]+‐Kation enthält unsymmetrische μ‐F‐Brücken. Die Fluoronium‐Ionen wurden in Form ihrer [SbF6]−‐Salze erhalten und Raman‐ und 19F‐NMR‐spektroskopisch sowie durch Röntgenbeugung am Einkristall untersucht. Quantenchemische Rechnungen, sowohl für die isolierten Kationen in der Gasphase als auch für die Festkörper selbst, wurden durchgeführt. Populationsanalysen ergaben, dass die μ‐F‐Atome die am stärksten negativ partialgeladenen Atome der Kationen sind.

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

“…Some groups have started to work in this field again, leading to interesting compounds such as [Br 3 F 8 ][SbF 6 ], which has been published very recently. [14] Thea pplications of polyhalogen anions range from regioselective halogenation reactions to green chemistry with af ocus on metal recycling.M oreover, polyhalogen anions play ak ey role in electrochemistry,f or example in zinc-bromine redox flow batteries.N evertheless,i tc an be expected that the number of applications will still increase as our knowledge of polyhalogen chemistry expands.…”

“…The tetracosabromine dianion, [Br 24 ] 2À : Theh ighest polybromine dianion network known to date is the tetracosabromide,[ Br 24 ] 2À . [34] Maschmeyer et al synthesized [(n-Bu) 4 P] 2 [Br 24 ]b yv olumetric addition of bromine to an eutectic mixture of [(n-Bu) 4 ]Br and [P 6,6,6,14 ]Br.T he resulting dianion ( Figure 30) has properties in common with the [Br 11 ·Br 2 ] À anions of Haller. [102] Thec entral bromide is fivefold-coordinated by Br 2 units and af urther bromine molecule is end-on-coordinated.…”

“…Yearly production and use of the halogens fluorine, chlorine, bromine, and iodine. [1] ogens and polyhalogens.N eutral interhalogen species (e.g., BrCl, BrF 3 ,C lF 5 ,I 2 Cl 6 ,I F 7 ), cationic (e.g., [I 3 ] + , [10] [Cl 3 ] + , [11] [Br 5 ] + , [12] [I 15 ] 3+ , [13] [Br 3 F 8 ] + [14] ), and anionic polyhalogen species are known. In contrast to the presently underexplored polyhalogen cations,o fw hich only af ew examples exist, the diversity of polyhalogen anions is significantly greater.…”

Synthesis and characterization of the pyridine—bromine trifluoride (1/1) complex, [py∙BrF3]

“…Therefore, the whole molecule is not planar. The square planar atomic environment around the Br atom is typical for Br in oxidation state +III and can be observed in compounds containing [BrF2] + , [17][18][19] [Br2F5] + , [20,21] [Br3F8] + [20,21] cations, [BrF4] -, [22][23][24][25][26][27] [Br2F7] -, [28] [Br3F10] - [28] anions, as well as in solid BrF3. [29] The F1-Br1-N1 angle in [py•BrF3] is exactly 180° as all three atoms reside on the crystallographic two-fold rotation axis.…”

Polyhalogen‐ und Polyinterhalogen‐Anionen von Fluor bis Iod

“…B. [I 3 ] + , [10] [Cl 3 ] + , [11] [Br 5 ] + , [12] [I 15 ] 3+ , [13] [Br 3 F 8 ] + [14] )und anionische Polyhalogene.Während von den weniger untersuchten Polyhalogen-Kationen nur wenige bekannt sind, ist die Vielfalt der Polyhalogen-Anionen weitaus grçßer. Dabei soll nicht unerwähnt bleiben, dass beträchtliche Anstrengungen unternommen werden, um auch ungewçhnliche Polyhalogen-Kationen herzustellen, z.…”