Methanium

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Methanium
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In chemistry, methanium is a complex positive ion with formula Template:Chem2 (metastable transitional form, a carbon atom covalently bonded to five hydrogen atoms) or Template:Chem2 (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.

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 (Template:Chem2), by analogy with the derivation of ammonium ion (Template:Chem2) from ammonia (Template:Chem2).

Structure

Fluxional methanium can be visualised as a Template:Chem2 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 Template:Chem2 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 Template:Chem2 molecule can continuously exchange positions with the three hydrogen atoms in the Template:Chem2 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 Template:Chem2 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 Template:Chem2 in hydrogen fluoride HF).[10]

At about 270 Pa of pressure and ambient temperature, the methane ion Template:Chem2 will react with neutral methane to yield methanium and a methyl radical:[11]

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The methanium ion can also be made in the gas phase via the reaction of methane and an Template:Chem2 ion (i.e. a proton).Script error: No such module "Unsubst".

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Stability and reactions

The cations obtained by reaction of methane with Template:Chem2, 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

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See also

References

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  2. V. L. Talrose and A. K. Lyubimova, Dokl. Akad. Nauk SSSR 86, 909-912 (1952) (In Russian: Тальрозе, В. Л., and А. К. Любимова. "Вторичные процессы в ионном источнике масс-спектрометра." ДАН СССР 86 (1952): 909-912)
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