Methanium

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Methanium
Chemdg methonium 1pos.svg
"True" methanium, the metastable transitional state [CH5]+
Methonium.svg
Fluxional methanium, [CH3(H2)]+
Names
IUPAC name
Methanium
Other names
carbonium (discouraged due to multiple definitions) [1]
Identifiers
3D model (JSmol)
PubChem CID
  • true methanium:InChI=1S/CH5/h1H5/q+1
    Key: PXOFOHGGCICFQD-UHFFFAOYSA-N
  • fluxional methanium:InChI=1S/CH5/c1-2/h2H,1H3/q+1
    Key: AJLDAZFHECSILY-UHFFFAOYSA-N
  • true methanium:[C+H5]
  • fluxional methanium:[CH3+].[HH]
Properties
CH+5
Molar mass 17.051 g·mol−1
Conjugate base Methane
Structure
trigonal bipyramidal
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

In chemistry, methanium is a complex positive ion with formula [ C H 5]+ (metastable transitional form, a carbon atom covalently bonded to five hydrogen atoms) or [CH3(H2)]+ (fluxional form, namely a molecule with one carbon atom covalently bonded to three hydrogen atoms and one dihydrogen molecule), bearing a +1 electric charge. It is a superacid and one of the onium ions, indeed the simplest carbonium ion.

Contents

It is highly unstable and highly reactive even upon having a complete octet, thus granting its superacidic properties.

Methanium can be produced in the laboratory as a rarefied gas or as a dilute species in superacids. It was prepared for the first time in 1950 and published in 1952 by Victor Talrose and his assistant Anna Konstantinovna Lyubimova. [2] [3] It occurs as an intermediate species in chemical reactions.

The methanium ion is named after methane (CH4), by analogy with the derivation of ammonium ion (NH+4) from ammonia (NH3).

Structure

Fluxional methanium can be visualised as a CH+3 carbenium ion with a molecule of hydrogen interacting with the empty orbital in a 3-center-2-electron bond. The bonding electron pair in the H2 molecule is shared between the two hydrogen and one carbon atoms making up the 3-center-2-electron bond. [4]

The two hydrogen atoms in the H2 molecule can continuously exchange positions with the three hydrogen atoms in the CH+3 ion (a conformation change called pseudorotation, specifically the Berry mechanism). The methanium ion is therefore considered a fluxional molecule. The energy barrier for the exchange is quite low and occurs even at very low temperatures. [5] [6]

Infrared spectroscopy has been used to obtain information about the different conformations of the methanium ion. [7] [8] [9] The IR spectrum of plain methane has two C-H bands from symmetric and asymmetric stretching at around 3000 cm−1 and two bands around 1400 cm−1 from symmetrical and asymmetric bending vibrations. In the spectrum of CH+5 three asymmetric stretching vibrations are present around 2800–3000 cm−1, a rocking vibration at 1300 cm−1, and a bending vibration at 1100 1300 cm−1.

Preparation

Methanium can be prepared from methane by the action of very strong acids, such as fluoroantimonic acid (antimony pentafluoride SbF5 in hydrogen fluoride HF). [10]

At about 270 Pa of pressure and ambient temperature, the methane ion CH+4 will react with neutral methane to yield methanium and a methyl radical: [11]

CH+4 + CH4 → CH+5 + CH3

The methanium ion can also be made in the gas phase via the reaction of methane and an H+ ion (i.e. a proton).[ citation needed ]

CH4 + H+(g) → CH+5

Stability and reactions

The cations obtained by reaction of methane with SbF5 + HF, including methanium, are stabilized by interactions with the HF molecules.

At low pressures (around 1 mmHg) and ambient temperatures, methanium is unreactive towards neutral methane. [11]

Further reading

See also

Related Research Articles

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3
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3
, methanium CH+
5
and vinyl C
2
H+
3
cations. Occasionally, carbocations that bear more than one positively charged carbon atom are also encountered.

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2
H+
7
. It can be described as a molecule of ethane with one extra proton, that gives it a +1 electric charge.

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References

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