Tetrafluoroammonium Salts

Nikitin, I V; Rosolovskii, V. Ya.

doi:10.1070/rc1985v054n05abeh003068

Cited by 14 publications

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“…In accord with previous reports, [46,53] the NF 4 C radical has am etastable minimum-energy structure with a C 3v NF 3 unit with three short (1.369 ), strong N À Fb onds and one long (2.8 ), very weak N À Fbond, and is unbound with respect to NF 3 and Fwith abond dissociation energy of À2.0 kcal mol À1 (Figure 3). This implies that under the reaction conditions of the thermal synthesis (150-250 8 8C), the NF 4 C radical would have no stability at all and would spontaneously lose an FC atom.…”

supporting

confidence: 91%

“…[2] During the next 18 years,m ore than 30 different NF 4 + salts were prepared, as shown in ac omprehensive review of the field by Nikitin and Rosolovskii. [3] Although their review gives ac omplete summary of the chemistry of NF 4 + up to 1983, the history of its discovery has never been documented.…”

mentioning

confidence: 99%

“…In the 1960s,much of the government-sponsored research was classified, and the first open publication frequently does not reflect the original discoverers.T ypical examples are ClF 5 , NF 3 O, and ClF 3 O, which were first prepared and characterized at Rocketdyne,b ut are credited in the literature and textbooks to other researchers who reported them first in the open literature.…”

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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 4 + cation has been knownf or 51 years,a nd its formation mechanism from NF 3 , F 2 ,a nd as trong 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 Fatoms from F 2 ,a nd also that the NF 3 + cation is akey intermediate.However,itwas not possible to establish whether the second step involved the reaction of aFatom with either NF 3 or the Lewis acid (LA). To distinguish between these two alternatives,acomputational study of the NF 4 ,SbF 6 ,AsF 6 ,and BF 4 radicals was carried out. Whereas the heats of reaction are small and similar for the NF 4 and LAF radicals,a tt he reaction temperatures,o nly the LAF radicals possess sufficient thermal stability to be viable species. Most importantly,t he ability of the LAF radicals to oxidize NF 3 to NF 3 + 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.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.

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confidence: 99%

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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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“…However, even with a Lewis acid stronger than SbF 5 the synthesis would still present a major challenge because the ArF 2 parent molecule is vibrationally unstable. Therefore, any synthesis of [ArF] + salts will require synthetic methods analogous to those previously used for the syntheses of cations derived from nonexisting parent molecules, such as [NF 4 ] + ,32, 33 which involve the use of elemental fluorine in combination with suitable activation energy sources.…”

Section: The First Ground State Argon Compound With Covalent Argon–hementioning

confidence: 99%

A Renaissance in Noble Gas Chemistry

Christe

2001

Angew. Chem. Int. Ed.

130

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“…Trotzdem wird auch mit einer Lewis‐Säure stärker als SbF 5 die Synthese eine große Herausforderung bedeuten, denn das Stammolekül ArF 2 ist schwingungslabil. Deswegen wird jede Synthese von ArF + ‐Salzen Methoden erfordern, die – analog zu den Synthesemethoden von Kationen aus nichtexistenten Stammolekülen wie NF 4 + 32, 33 – auf dem Einsatz von elementarem Fluor in Kombination mit geeigneten Aktivierungsenergie‐Quellen beruhen.…”

Section: Die Erste Ar‐verbindung Im Grundzustand Mit Kovalenten Ar‐heunclassified

Die Renaissance der Edelgaschemie

Christe

2001

Angew. Chem.

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Obwohl stabile Edelgasverbindungen mindestens seit 1902 vorausgesagt worden waren, lieûen erfolglose Syntheseversuche die weit verbreitete Ansicht entstehen, dass sich Edelgase chemisch nicht nur edel, sondern völlig inert verhalten. [1] Diese Einschätzung wurde dogmaartig in fast allen Lehrbüchern vertreten und entmutigte über eine lange Zeit Forscher auf diesem Gebiet zu arbeiten. Dies änderte sich erst 1962, als Bartlett in Kanada [2] die erste stabile Edelgasverbindung, XePtF 6 , entdeckte. Diese Endeckung löste weltweit eine Lawine der Begeisterung los ± sehr bald wurden viele neue Xe-, Rn-sowie Kr-Verbindungen hergestellt und charakterisiert. Rund dreiûig Jahre später, nachdem viele Arbeiten zu Edelgasen erschienen waren, gab es kaum noch neue Resultate, und für die meisten Chemiker galt die Edelgaschemie als abgeschlossenes Kapitel. Dass sie aber nach wie vor voller Überraschungen steckt, zeigte jüngst eine Welle Aufsehen erregender Ergebnisse, die möglicherweise eine Renaissance dieses Forschungsgebiets einläutet.Die gegenwärtigen Entwicklungen lassen sich in vier Kategorien einteilen, die in den folgenden Abschnitten dargestellt werden, wobei exemplarisch kürzlich publizierte oder derzeit laufende Forschungsaktivitäten vorgestellt werden: 1) Aufbau von entweder neuartigen Xe II -Heteroatom-oder bekannten Xe-Heteroatom-Verknüpfungen unter Beteiligung höherer Oxidationsstufen des Xenons 2) Eignung des XeF 2 als Ligand für zahlreiche nackte Metallionen 3) Eignung des Xenons als Komplexligand 4) Beobachtung der ersten Ar-Verbindung im Grundzustand mit kovalenten Ar-Heteroatom-Bindungen

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Tetrafluoroammonium Salts

Cited by 14 publications

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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

A Renaissance in Noble Gas Chemistry

Die Renaissance der Edelgaschemie

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Tetrafluoroammonium Salts

Cited by 14 publications

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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

A Renaissance in Noble Gas Chemistry

Die Renaissance der Edelgaschemie

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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