Tetrafluoroammonium

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Tetrafluoroammonium
Tetrafluoroammonium ion.png
2D model of the tetrafluoroammonium ion
Names
IUPAC name
Tetrafluoroammonium
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
2028
PubChem CID
  • InChI=1S/F4N/c1-5(2,3)4/q+1
    Key: LDOAUKNENSIPAZ-UHFFFAOYSA-N
  • [N+](F)(F)(F)F
Properties
F4N+
Molar mass 90.000 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

The tetrafluoroammonium cation (also known as perfluoroammonium) is a positively charged polyatomic ion with chemical formula NF+
4. It is equivalent to the ammonium ion where the hydrogen atoms surrounding the central nitrogen atom have been replaced by fluorine. [1] Tetrafluoroammonium ion is isoelectronic with tetrafluoromethane CF
4, trifluoramine oxide ONF
3, tetrafluoroborate BF−
4 anion and the tetrafluoroberyllate BeF2−
4 anion.

Contents

The tetrafluoroammonium ion forms salts with a large variety of fluorine-bearing anions. These include the bifluoride anion (HF−
2), tetrafluorobromate (BrF−
4), metal pentafluorides (MF−
5 where M is Ge, Sn, or Ti), hexafluorides (MF−
6 where M is P, As, Sb, Bi, or Pt), heptafluorides (MF−
7 where M is W, U, or Xe), octafluorides (XeF2−
8), [2] various oxyfluorides (MF
5O−
 where M is W or U; FSO−
3 , BrF
4O−
), and perchlorate (ClO−
4). [3] Attempts to make the nitrate salt, NF
4NO
3, were unsuccessful because of quick fluorination: NF+
4 + NO−
3 → NF
3 + FONO
2. [4]

Structure

The geometry of the tetrafluoroammonium ion is tetrahedral, with an estimated nitrogen-fluorine bond length of 124  pm. All fluorine atoms are in equivalent positions. [5]

Synthesis

Tetrafluoroammonium salts are prepared by oxidising nitrogen trifluoride with fluorine in the presence of a strong Lewis acid which acts as a fluoride ion acceptor. The original synthesis by Tolberg, Rewick, Stringham, and Hill in 1966 employs antimony pentafluoride as the Lewis acid: [5]

NF
3 + F
2 + SbF
5 → NF
4SbF
6

The hexafluoroarsenate salt was also prepared by a similar reaction with arsenic pentafluoride at 120 °C: [5]

NF
3 + F
2 + AsF
5 → NF
4AsF
6

The reaction of nitrogen trifluoride with fluorine and boron trifluoride at 800 °C yields the tetrafluoroborate salt: [6]

NF
3 + F
2 + BF
3 → NF
4BF
4

NF+
4 salts can also be prepared by fluorination of NF
3 with krypton difluoride (KrF
2) and fluorides of the form MF
n, where M is Sb, Nb, Pt, Ti, or B. For example, reaction of NF
3 with KrF
2 and TiF
4 yields [NF+
4]
2TiF2−
6. [7]

Many tetrafluoroammonium salts can be prepared with metathesis reactions.

Reactions

Tetrafluoroammonium salts are extremely hygroscopic. The NF+
4 ion, when dissolved in water, readily decomposes into NF
3, H
2F+
, and oxygen gas. Some hydrogen peroxide (H
2O
2) is also formed during this process: [5]

NF+
4 + H
2O → NF
3 + H
2F+
 + 1⁄2O
2
NF+
4 + 2 H
2O → NF
3 + H
2F+
 + H
2O
2

Reaction of NF+
4SbF−
6 with alkali metal nitrates yields fluorine nitrate, FONO
2. [4]

Properties

Because NF+
4 salts are destroyed by water, water cannot be used as a solvent. Instead, bromine trifluoride, bromine pentafluoride, iodine pentafluoride, or anhydrous hydrogen fluoride can be used. [8]

Tetrafluoroammonium salts usually have no colour. However, some are coloured due to other elements in them. (NF+
4)
2CrF2−
6, (NF+
4)
2NiF2−
6 and (NF+
4)
2PtF2−
6 have a red colour, while (NF+
4)
2MnF2−
6, NF+
4UF−
7, NF+
4UOF−
5 and NF+
4XeF−
7 are yellow. [8]

Applications

NF+
4 salts are important for solid propellant NF
3–F
2 gas generators. They are also used as reagents for electrophilic fluorination of aromatic compounds in organic chemistry. [5] As fluorinating agents, they are also strong enough to react with methane. [9]

See also

Related Research Articles

In chemistry, noble gas compounds are chemical compounds that include an element from the noble gases, group 18 of the periodic table. Although the noble gases are generally unreactive elements, many such compounds have been observed, particularly involving the element xenon.

In chemistry, an interhalogen compound is a molecule which contains two or more different halogen atoms and no atoms of elements from any other group.

<span class="mw-page-title-main">Manganese(III) fluoride</span> Chemical compound

Manganese(III) fluoride (also known as Manganese trifluoride) is the inorganic compound with the formula MnF3. This red/purplish solid is useful for converting hydrocarbons into fluorocarbons, i.e., it is a fluorination agent. It forms a hydrate and many derivatives.

<span class="mw-page-title-main">Chlorine pentafluoride</span> Chemical compound

Chlorine pentafluoride is an interhalogen compound with formula ClF5. This colourless gas is a strong oxidant that was once a candidate oxidizer for rockets. The molecule adopts a square pyramidal structure with C4v symmetry, as confirmed by its high-resolution 19F NMR spectrum. It was first synthesized in 1963.

<span class="mw-page-title-main">Nitrogen trifluoride</span> Chemical compound

Nitrogen trifluoride is the inorganic compound with the formula. It is a colorless, non-flammable, toxic gas with a slightly musty odor. In contrast with ammonia, it is nonbasic. It finds increasing use within the manufacturing of flat-panel displays, photovoltaics, LEDs and other microelectronics. NF
3 is a greenhouse gas, with a global warming potential (GWP) 17,200 times greater than that of CO
2 when compared over a 100-year period.

<span class="mw-page-title-main">Cobalt(III) fluoride</span> Chemical compound

Cobalt(III) fluoride is the inorganic compound with the formula CoF3. Hydrates are also known. The anhydrous compound is a hygroscopic brown solid. It is used to synthesize organofluorine compounds.

Antimony pentafluoride is the inorganic compound with the formula SbF5. This colourless, viscous liquid is a strong Lewis acid and a component of the superacid fluoroantimonic acid, formed upon mixing liquid HF with liquid SbF5 in 1:1 ratio. It is notable for its strong Lewis acidity and the ability to react with almost all known compounds.

<span class="mw-page-title-main">Tetrafluoroborate</span> Anion

Tetrafluoroborate is the anion BF−
4. This tetrahedral species is isoelectronic with tetrafluoroberyllate (BeF2−
4), tetrafluoromethane (CF4), and tetrafluoroammonium (NF+
4) and is valence isoelectronic with many stable and important species including the perchlorate anion, ClO−
4, which is used in similar ways in the laboratory. It arises by the reaction of fluoride salts with the Lewis acid BF3, treatment of tetrafluoroboric acid with base, or by treatment of boric acid with hydrofluoric acid.

Xenon compounds are compounds containing the element xenon (Xe). After Neil Bartlett's discovery in 1962 that xenon can form chemical compounds, a large number of xenon compounds have been discovered and described. Almost all known xenon compounds contain the electronegative atoms fluorine or oxygen. The chemistry of xenon in each oxidation state is analogous to that of the neighboring element iodine in the immediately lower oxidation state.

<span class="mw-page-title-main">Selenium tetrafluoride</span> Chemical compound

Selenium tetrafluoride (SeF4) is an inorganic compound. It is a colourless liquid that reacts readily with water. It can be used as a fluorinating reagent in organic syntheses (fluorination of alcohols, carboxylic acids or carbonyl compounds) and has advantages over sulfur tetrafluoride in that milder conditions can be employed and it is a liquid rather than a gas.

<span class="mw-page-title-main">Xenon oxytetrafluoride</span> Chemical compound

Xenon oxytetrafluoride is an inorganic chemical compound. It is an unstable colorless liquid with a melting point of −46.2 °C that can be synthesized by partial hydrolysis of XeF
6, or the reaction of XeF
6 with silica or NaNO
3:

<span class="mw-page-title-main">Dioxygenyl</span> Chemical compound

The dioxygenyl ion, O+
2, is a rarely-encountered oxycation in which both oxygen atoms have a formal oxidation state of +1/2. It is formally derived from oxygen by the removal of an electron:

<span class="mw-page-title-main">Fluorine perchlorate</span> Chemical compound

Fluorine perchlorate, also called perchloryl hypofluorite is the rarely encountered chemical compound of fluorine, chlorine, and oxygen with the chemical formula ClO
4F or FOClO
3. It is an extremely unstable gas that explodes spontaneously and has a penetrating odor.

<span class="mw-page-title-main">Chromyl fluoride</span> Chemical compound

Chromyl fluoride is an inorganic compound with the formula CrO2F2. It is a violet-red colored crystalline solid that melts to an orange-red liquid.

Nitrogen pentafluoride (NF5) is a theoretical compound of nitrogen and fluorine that is hypothesized to exist based on the existence of the pentafluorides of the atoms below nitrogen in the periodic table, such as phosphorus pentafluoride. Theoretical models of the nitrogen pentafluoride molecule are either a trigonal bipyramidal covalently bound molecule with symmetry group D3h, or NF+
4F−, which would be an ionic solid.

Fluorine forms a great variety of chemical compounds, within which it always adopts an oxidation state of −1. With other atoms, fluorine forms either polar covalent bonds or ionic bonds. Most frequently, covalent bonds involving fluorine atoms are single bonds, although at least two examples of a higher order bond exist. Fluoride may act as a bridging ligand between two metals in some complex molecules. Molecules containing fluorine may also exhibit hydrogen bonding. Fluorine's chemistry includes inorganic compounds formed with hydrogen, metals, nonmetals, and even noble gases; as well as a diverse set of organic compounds. For many elements the highest known oxidation state can be achieved in a fluoride. For some elements this is achieved exclusively in a fluoride, for others exclusively in an oxide; and for still others the highest oxidation states of oxides and fluorides are always equal.

<span class="mw-page-title-main">Fluorine azide</span> Chemical compound

Fluorine azide or triazadienyl fluoride is a yellow green gas composed of nitrogen and fluorine with formula FN3. Its properties resemble those of ClN3, BrN3, and IN3. The bond between the fluorine atom and the nitrogen is very weak, leading to this substance being very unstable and prone to explosion. Calculations show the F–N–N angle to be around 102° with a straight line of 3 nitrogen atoms.

<span class="mw-page-title-main">Trifluoramine oxide</span> Chemical compound

Trifluoramine oxide or Nitrogen trifluoride oxide (F3NO) is an inorganic molecule with strong fluorinating powers.

<span class="mw-page-title-main">Chlorine trifluoride oxide</span> Chemical compound

Chlorine oxide trifluoride or chlorine trifluoride oxide is a corrosive liquid molecular compound with formula ClOF3. It was developed secretly as a rocket fuel oxidiser.

<span class="mw-page-title-main">Hexafluoroarsenate</span> Chemical compound

The hexafluoroarsenate anion is a chemical species with formula AsF−6. Hexafluoroarsenate is relatively inert, being the conjugate base of the notional superacid hexafluoroarsenic acid.

References

  1. ↑ Nikitin, I. V.; Rosolovskii, V. Y. (1985). "Tetrafluoroammonium Salts". Russian Chemical Reviews. 54 (5): 426. Bibcode:1985RuCRv..54..426N. doi:10.1070/RC1985v054n05ABEH003068. S2CID   250864362.
  2. ↑ Christe, K. O.; Wilson, W. W. (1982). "Perfluoroammonium and alkali-metal salts of the heptafluoroxenon(VI) and octafluoroxenon(VI) anions". Inorganic Chemistry. 21 (12): 4113–4117. doi:10.1021/ic00142a001.
  3. ↑ Christe, K. O.; Wilson, W. W. (1986). "Synthesis and characterization of tetrafluoroammonium(1+) tetrafluorobromate(1-) and tetrafluoroammonium(1+) tetrafluorooxobromate(1-)". Inorganic Chemistry. 25 (11): 1904–1906. doi:10.1021/ic00231a038.
  4. 1 2 Hoge, B.; Christe, K. O. (2001). "On the stability of NF+
    4    NO−
    3     and a new synthesis of fluorine nitrate". Journal of Fluorine Chemistry. 110 (2): 87–88. doi:10.1016/S0022-1139(01)00415-8.
  5. 1 2 3 4 5 Sykes, A. G. (1989). Advances in Inorganic Chemistry. Academic Press. ISBN   0-12-023633-8.
  6. ↑ Patnaik, Pradyot (2002). Handbook of inorganic chemicals. McGraw-Hill Professional. ISBN   0-07-049439-8.
  7. ↑ John H. Holloway; Eric G. Hope (1998). A. G. Sykes (ed.). Advances in Inorganic Chemistry . Academic Press. pp.  60–61. ISBN   0-12-023646-X.
  8. 1 2 Sykes, A. G. (1989-07-17). Advances in Inorganic Chemistry. Academic Press. p. 154. ISBN   9780080578828 . Retrieved 22 June 2014.
  9. ↑ Olah, George A.; Hartz, Nikolai; Rasul, Golam; Wang, Qi; Prakash, G. K. Surya; Casanova, Joseph; Christe, Karl O. (1994-06-01). "Electrophilic Fluorination of Methane with "F+" Equivalent N2F+ and NF4+ Salts". Journal of the American Chemical Society. 116 (13): 5671–5673. doi:10.1021/ja00092a018. ISSN   0002-7863.
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