Soluble Fluoridobromates as Well‐Behaved Strong Fluorination Reagents

Schmid, Jonas R.; Pröhm, Patrick; Voßnacker, Patrick; Thiele, Günther; Ellwanger, Mathias; Steinhauer, Simon; Riedel, Sebastian

doi:10.1002/ejic.202000847

Cited by 7 publications

(6 citation statements)

References 31 publications

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“…Additionally, the symmetric Br−F stretching mode is observed at 477 cm −1 as the dominant vibration in the spectrum. This is in excellent agreement with the a 1g and b 1g vibrations of [BrF 4 ] − at 519 cm −1 and 442 cm −1 [23] . In comparison with the Br I species 2 the ν sy (BrO) mode is slightly blue shifted by 8 cm −1 due to the stronger bond formation which is in line with the structural data of the crystal structure.…”

Section: Resultssupporting

confidence: 86%

“…This is in excellent agreement with the a 1g and b 1g vibrations of [BrF 4 ] − at 519 cm −1 and 442 cm −1 . [23] In comparison with the Br I species 2 the ν sy (BrO) mode is slightly blue shifted by 8 cm −1 due to the stronger bond formation which is in line with the structural data of the crystal structure. The NPA analysis shows a charge of +1.40 at the bromine which is significantly increased in comparison to 2 (+0.31), however, it is comparable to the natural charge of Br in [BrF 4 ] − (+1.46).…”

Section: Resultssupporting

confidence: 80%

“…The Br−F bonds have a length of 189.3(2) pm (calc: 190.1 pm). This is very similar to the Br−F bond lengths in [NEt 3 Me][BrF 4 ] with 188.93(1) pm to 190.47(1) pm [23] . Therefore we assume that the bonding situation in the anion of 2 is closely related to the bonding situation in [BrF 4 ] − .…”

Section: Resultssupporting

confidence: 75%

“…The reaction is reminiscent of the fluorination of Cl − and Br − to the tetrafluorido halogenates(III) under similar conditions. [ 22 , 23 ] Interestingly, we obtained the same compound from the ligand exchange reaction between [NEt 4 ][BrF 4 ] and ClOC 4 F 9 under elimination of two equivalents of ClF (Eq. (6)).…”

Section: Resultsmentioning

confidence: 99%

“…This is very similar to the Br−F bond lengths in [NEt 3 Me][BrF 4 ] with 188.93(1) pm to 190.47(1) pm. [23] Therefore we assume that the bonding situation in the anion of 2 is closely related to the bonding situation in [BrF 4 ] − . This can also be deduced from the Raman spectrum (Figure S5).…”

Section: Resultsmentioning

confidence: 99%

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Investigation of Bis(Perfluoro‐tert‐Butoxy) Halogenates(I/III)

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A systematic study of halogenate(I/III) anions with polyatomic ligands is presented. The bis(perfluoro‐tert‐butoxy) halogenates(I) [X(OC4F9)2]−, X=Cl, Br, I, of chlorine, bromine, and iodine are prepared as their tetraethylammonium salts and characterized with IR, Raman, and NMR spectroscopic methods, as well as single‐crystal X‐ray diffraction analyses. Spectroscopical data are supported by quantum‐chemical calculations. Additionally, the bonding situation of the species in question are analyzed and discussed. Furthermore, the oxidation to the corresponding halogenate(III) derivatives was studied. For [Br(OC4F9)2]−, oxidation with elemental fluorine gave [BrF2(OC4F9)2]−. Iodide was directly oxidized by ClOC4F9 to the IIII species [I(OC4F9)4]−, which is a surprisingly inert anion that might be used as a weakly coordinating anion (WCA) in the future. For [Cl(OC4F9)2]−, the decomposition products of the synthetic approaches towards a chlorine(III) system were analyzed.

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Section: Resultssupporting

confidence: 86%

Section: Resultssupporting

confidence: 80%

Section: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 3 more Smart Citations

Investigation of Bis(Perfluoro‐tert‐Butoxy) Halogenates(I/III)

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Rupf

et al. 2021

Chemistry A European J

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Synthese des Hexachlorosulfat(IV)‐Dianions ermöglicht durch Polychloridchemie

et al. 2022

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Es wird über die Herstellung und strukturelle Charakterisierung von [NEt3Me]2[SCl6] berichtet. Diese Verbindung ist das erste Beispiel für ein [SCl6]2−‐Dianion und für ein Halogensulfat‐Anion vom Typ [SxXy]z− im Allgemeinen. Das [SCl6]2− gehört zur Gruppe der AB6E‐Systeme mit 14 Valenzelektronen und bildet im festen Zustand eine oktaedrische Struktur aus. Interessanterweise führt die Co‐Kristallisation von CH2Cl2 zur Bildung von [NEt3Me]2[SCl6]⋅4 CH2Cl2 in dem das [SCl6]2−‐Dianion eine C4v‐Symmetrie aufweist. Wie quantenchemische Berechnungen nahelegen, wird die Verzerrung der Struktur nicht durch ein stereochemisch aktives freies Elektronenpaar, sondern durch verstärkte Wasserstoffbrückenbindungen mit CH2Cl2 verursacht. Bei erhöhten Temperaturen zersetzt sich [NEt3Me]2[SCl6] in verschiedene Schwefel‐Chlor‐Verbindungen, wie sich durch Raman‐Spektroskopie nachweisen lässt. Abkühlen auf Raumtemperatur führt zur selektiven Bildung von [NEt3Me]2[SCl6], das mit dem gut untersuchten SCl4 vergleichbar ist.

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Synthesis of a Hexachloro Sulfate(IV) Dianion Enabled by Polychloride Chemistry

et al. 2022

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The preparation and structural characterization of [NEt3Me]2[SCl6] is described, which is the first example of a [SCl6]2− dianion and of a halosulfate anion of the type [SxXy]z− in general. This dianion belongs to the group of 14‐valence electron AB6E systems and forms an octahedral structure in the solid‐state. Interestingly, co‐crystallization with CH2Cl2 affords [NEt3Me]2[SCl6]⋅4 CH2Cl2 containing [SCl6]2− dianions with C4v symmetry. As suggested by quantum‐chemical calculations, the distortion of the structure is not caused by a stereochemically active lone pair but by enhanced hydrogen bonding interactions with CH2Cl2. At elevated temperatures, [NEt3Me]2[SCl6] decomposes to various sulfur chlorine compounds as shown by Raman spectroscopy. Cooling back to room temperature results in the selective formation of [NEt3Me]2[SCl6] which is comparable to the well‐studied SCl4.

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Soluble Fluoridobromates as Well‐Behaved Strong Fluorination Reagents

Cited by 7 publications

References 31 publications

Investigation of Bis(Perfluoro‐tert‐Butoxy) Halogenates(I/III)

Investigation of Bis(Perfluoro‐tert‐Butoxy) Halogenates(I/III)

Synthese des Hexachlorosulfat(IV)‐Dianions ermöglicht durch Polychloridchemie

Synthesis of a Hexachloro Sulfate(IV) Dianion Enabled by Polychloride Chemistry

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