The synthesis of the perfluoroammonium cation, NF4+

Tolberg, W. E.; Rewick, Robert T.; Stringham, Roger S.; Hill, Marion E.

doi:10.1021/ic50052a020

Cited by 53 publications

(11 citation statements)

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“…Instead, the SRI group requested the Navy to classify the Stauffer work while they had their own work declassified at the same time and rushed their paper to Inorganic Nuclear Chemistry Letters (INCL) for publication. Only through the intervention of the editor of INCL and a rapid repeal of the Navy classification was the Stauffer group able to make the same issue of INCL as the SRI group . Clearly, the first synthesis of an NF 4 + salt must be credited to the Stauffer group, as confirmed in a 1968 book by Lawless and Smith who had full access to all of the pertinent government reports.…”

Section: Figurementioning

confidence: 99%

“…As the 15 kV glow discharge, used for the original synthesis of [NF 4 ] + [AsF 6 ] − , could have easily provided the energy required to produce either NF 3 + , F 2 + , or F + as the primary reagents, an ionic mechanism involving these ions seemed reasonable . However, as the thermal high‐pressure syntheses of NF 4 + salts are not capable of generating these ions, an alternate mechanism was subsequently proposed that invoked the heterolytic fission of F 2 by the simultaneous action of a highly fluorinated Lewis acid (LA) and a highly fluorinated base [Eq. ].

true NF_{3} + \overset{δ +}{normalF} - \overset{δ -}{normalF} + LA \to [NF_{4}]^{+} [LAF]^{-}

…”

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%

true NF_{3} + \overset{δ +}{normalF} - \overset{δ -}{normalF} + LA \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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Section: Introductionmentioning

confidence: 99%

“…One of the first mentions of the M(SbF 6 ) 2 salt dates back to 1967, when a reaction between a mixture of NF 3 , F 2 and SbF 5 heated under pressure was reported to cause NF 4 SbF 6 to be contaminated with Ni(SbF 6 ) 2 as an impurity. [1] The source of nickel was Monel reaction vessel. High-temperature fluorination involving SbF 5 is mostly carried out in reaction vessels made of nickel or nickel-copper alloys such as Monel, and the final products could be contaminated with Ni(SbF 6 ) 2 .…”

Section: Introductionmentioning

confidence: 99%

Crystal Structures of Hexafluoridoantimonate(V) Salts of d‐block Metals in Oxidation State +2

Mazej

Goreshnik

2022

Eur J Inorg Chem

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The crystal structures of the M(SbF6)2 salts (M=Cu, Pd) are isotypic (Type I). They crystallize in the triclinic space group P1‾ , Z=1 at 150 K. M2+ cations lying in the same plane are connected via SbF6 units forming slabs. There are only van der Waals contacts of fluorine atoms between the adjacent slabs. Salts of M(SbF6)2 (M=Fe, Co, Zn) crystallize differently (Type II; space group P1‾ , Z=2 at 150 K). Their crystal structures are composed of M2+ cations interconnected by [SbF6]− anions – thus forming a three‐dimensional framework. The crystal structure of Fe(SbF6)2, determined at 240 K, is currently the only representative of the Type III. The main feature of this type is also a three‐dimensional framework consisting of M2+ cations and [SbF6]− anions. However, the mode of their association differs from that observed in Type II. The crystal structures of CuFSbF6 (orthorhombic space group Imma, Z=4 at 150 K) and AgFSbF6 (orthorhombic space group Pnma, Z=4 at 150 K) are not isotypic. The crystal structures of the by‐products H3ONi(SbF6)3 (orthorhombic space group Pnma, Z=4 at 150 K) and (O2)2Ag6CuF5(SbF6)11 ⋅ 2HF (triclinic space group P1‾ , Z=1 at 150 K) were determined. In the latter, HF is directly attached to an Ag(II) via a fluorine atom.

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“…Thef irst ionization potentials of NF 3 (13.00 eV), F 2 (15.70 eV), and F (17.42 eV) [10] are all very high and outside the range achievable by conventional chemistry.A st he 15 kV glow discharge,u sed for the original synthesis of [NF 4 ] + [AsF 6 ] À , [1] could have easily provided the energy required to produce either NF 3 + ,F 2 + ,o rF + as the primary reagents,a ni onic mechanism involving these ions seemed reasonable. [1,11] However,a st he thermal high-pressure syntheses [6,12] of NF 4 + salts are not capable of generating these ions,a n alternate mechanism was subsequently proposed [2] that invoked the heterolytic fission of F 2 by the simultaneous action of ah ighly fluorinated Lewis acid (LA) and ah ighly fluorinated base [Eq. (1)].…”

mentioning

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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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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The synthesis of the perfluoroammonium cation, NF4+

Cited by 53 publications

References 2 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

Crystal Structures of Hexafluoridoantimonate(V) Salts of d‐block Metals in Oxidation State +2

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

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The synthesis of the perfluoroammonium cation, NF4+

Cited by 53 publications

References 2 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

Crystal Structures of Hexafluoridoantimonate(V) Salts of d‐block Metals in Oxidation State +2

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

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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

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