New synthesis of tetrafluoroammonium(+) salts and its mechanistic interpretation involving a new and exceptionally powerful oxidizing species

Christie, Karl O.; Wilson, Richard D.; Axworthy, Arthur E.

doi:10.1021/ic50128a055

Cited by 19 publications

(2 citation statements)

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“…Most importantly, subsequent kinetic and ESR studies showed that the NF 3 + radical cation was a key intermediate both in the formation and the decomposition of NF 4 + salts. These data ruled out the heterolytic fission of F 2 [Eq.…”

Section: Figurementioning

confidence: 99%

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Formation Mechanism of NF₄⁺ Salts and Extraordinary Enhancement of the Oxidizing Power of Fluorine by Strong Lewis Acids

2017

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Although the existence of the NF cation has been known for 51 years, and its formation mechanism from NF , F , and a strong Lewis acid in the presence of an activation energy source had been studied extensively, the mechanism had not been established. Experimental evidence had shown that the first step involves the generation of F atoms from F , and also that the NF cation is a key intermediate. However, it was not possible to establish whether the second step involved the reaction of a F atom with either NF or the Lewis acid (LA). To distinguish between these two alternatives, a computational study of the NF , SbF , AsF , and BF radicals was carried out. Whereas the heats of reaction are small and similar for the NF and LAF radicals, at the reaction temperatures, only the LAF radicals possess sufficient thermal stability to be viable species. Most importantly, the ability of the LAF radicals to oxidize NF to NF demonstrates that they are extraordinary oxidizers. This extraordinary enhancement of the oxidizing power of fluorine with strong Lewis acids had previously not been fully recognized.

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Section: Figurementioning

confidence: 99%

“…or with NF 3 [Eq. ]

true normalF^{•} + NF_{3} \to NF_{4}^{•}

true NF_{4}^{•} + LA \to [NF_{3}]^{+}^{•} [LAF]^{-}

true [NF_{3}]^{+}^{•} [LAF]^{-} + normalF^{•} \to [NF_{4}]^{+} [LAF]^{-}

…”

Section: Figurementioning

confidence: 99%

Formation Mechanism of NF₄⁺ Salts and Extraordinary Enhancement of the Oxidizing Power of Fluorine by Strong Lewis Acids

2017

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Tetrafluoroammonium Salts

Wilson¹,

Schack²,

Wilson³

et al. 1986

Inorganic Syntheses

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Strukturchemie von Fluoriden und Oxidfluoriden der Nichtmetalle

Seppelt

1979

Angewandte Chemie

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Das Strukturverhalten der Nichtmetallfluoride und ‐oxidfluoride ergibt heute ein einheitliches Bild. Das gleiche gilt daher zum Teil auch für die Chemie dieser Verbindungen. Aussagen über das Strukturverhalten sind z. B. aus dem Elektronenpaarabstoßungsmodell (VSEPR‐Theorie) leicht abzuleiten. Regelmäßigkeiten der Anzahl von Liganden („Koordinationszahlen”︁) ermöglichen Strukturvorhersagen für größere Einheiten als isolierte Moleküle oder Ionen, was bei den Verbindungen der schwereren Elemente bedeutsam wird. – Die Verbindungsklasse findet ihre Grenze bei den leichteren Edelgasen, die selbst mit Fluor nur noch schwache oder keine Bindungen mehr eingehen.

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New synthesis of tetrafluoroammonium(+) salts and its mechanistic interpretation involving a new and exceptionally powerful oxidizing species

Cited by 19 publications

References 3 publications

Formation Mechanism of NF₄⁺ Salts and Extraordinary Enhancement of the Oxidizing Power of Fluorine by Strong Lewis Acids

Formation Mechanism of NF₄⁺ Salts and Extraordinary Enhancement of the Oxidizing Power of Fluorine by Strong Lewis Acids

Tetrafluoroammonium Salts

Strukturchemie von Fluoriden und Oxidfluoriden der Nichtmetalle

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New synthesis of tetrafluoroammonium(+) salts and its mechanistic interpretation involving a new and exceptionally powerful oxidizing species

Cited by 19 publications

References 3 publications

Formation Mechanism of NF4+ Salts and Extraordinary Enhancement of the Oxidizing Power of Fluorine by Strong Lewis Acids

Formation Mechanism of NF4+ Salts and Extraordinary Enhancement of the Oxidizing Power of Fluorine by Strong Lewis Acids

Tetrafluoroammonium Salts

Strukturchemie von Fluoriden und Oxidfluoriden der Nichtmetalle

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Product

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Formation Mechanism of NF₄⁺ Salts and Extraordinary Enhancement of the Oxidizing Power of Fluorine by Strong Lewis Acids

Formation Mechanism of NF₄⁺ Salts and Extraordinary Enhancement of the Oxidizing Power of Fluorine by Strong Lewis Acids