Lithium monoxide anion

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Lithium monoxide anion
Names
IUPAC name
Lithium monoxide anion
Other names
Lithate
Identifiers
3D model (JSmol)
  • InChI=1S/Li.O/q;-1
    Key: IXZJKKSRIFXCQD-UHFFFAOYSA-N
  • [Li]-[O-]
Properties
LiO
Molar mass 22.94 g·mol−1
Conjugate acid Lithium hydroxide
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Extremely corrosive
Related compounds
Related bases
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Lithium monoxide anion (LiO) is a superbase existing in the gas phase. It was the strongest known base until 2008, when the isomeric diethynylbenzene dianions were determined to have a higher proton affinity. The methanide ion CH3 was the strongest known base before lithium monoxide anion was discovered. [2]

Contents

LiO has a proton affinity of ~1782 kJ/mol. [3]

Synthesis of the lithium monoxide anion

The anion is prepared in a mass spectrometer by successive decarboxylation and decarbonylation of lithium oxalate anion under collision-induced dissociation (CID) conditions:

LiO−C(=O)−CO2 → LiO−C(=O) + CO2
LiO−C(=O) → LiO + CO

The above method to synthesize the lithium monoxide anion is inefficient and difficult to carry out. The required ion rapidly reacts with traces of moisture and molecular oxygen present in the air. The reaction is further intensified by the high pressure argon that is introduced into the instrument to carry out the CID step. [4]

Related Research Articles

<span class="mw-page-title-main">Alkali metal</span> Group of highly reactive chemical elements

The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr). Together with hydrogen they constitute group 1, which lies in the s-block of the periodic table. All alkali metals have their outermost electron in an s-orbital: this shared electron configuration results in their having very similar characteristic properties. Indeed, the alkali metals provide the best example of group trends in properties in the periodic table, with elements exhibiting well-characterised homologous behaviour. This family of elements is also known as the lithium family after its leading element.

In organic chemistry, a methyl group is an alkyl derived from methane, containing one carbon atom bonded to three hydrogen atoms, having chemical formula CH3. In formulas, the group is often abbreviated as Me. This hydrocarbon group occurs in many organic compounds. It is a very stable group in most molecules. While the methyl group is usually part of a larger molecule, bounded to the rest of the molecule by a single covalent bond, it can be found on its own in any of three forms: methanide anion, methylium cation or methyl radical. The anion has eight valence electrons, the radical seven and the cation six. All three forms are highly reactive and rarely observed.

In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to other atoms were fully ionic. It describes the degree of oxidation of an atom in a chemical compound. Conceptually, the oxidation state may be positive, negative or zero. While fully ionic bonds are not found in nature, many bonds exhibit strong ionicity, making oxidation state a useful predictor of charge.

<span class="mw-page-title-main">Base (chemistry)</span> Type of chemical substance

In chemistry, there are three definitions in common use of the word "base": Arrhenius bases, Brønsted bases, and Lewis bases. All definitions agree that bases are substances that react with acids, as originally proposed by G.-F. Rouelle in the mid-18th century.

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H), a hydrogen atom with two electrons. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

<span class="mw-page-title-main">Oxalate</span> Any derivative of oxalic acid; chemical compound containing oxalate moiety

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<span class="mw-page-title-main">Bisulfide</span> Inorganic anion containing one sulfur and one hydrogen atoms

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

Deltic acid is a chemical substance with the chemical formula C3O(OH)2. It can be viewed as a ketone and double enol of cyclopropene. At room temperature, it is a stable white solid, soluble in diethyl ether, that decomposes between 140 °C and 180 °C, and reacts slowly with water.

<span class="mw-page-title-main">Birch reduction</span> Organic reaction used to convert arenes to cyclohexadienes

The Birch reduction is an organic reaction that is used to convert arenes to 1,4-cyclohexadienes. The reaction is named after the Australian chemist Arthur Birch and involves the organic reduction of aromatic rings in an amine solvent with an alkali metal and a proton source. Unlike catalytic hydrogenation, Birch reduction does not reduce the aromatic ring all the way to a cyclohexane.

The carbonite ion is the double ionized ion of dihydroxymethylidene, with the chemical formula: CO2−
2
. Alkali metal salts, Li
2
CO
2
, K
2
CO
2
, Rb
2
CO
2
and Cs
2
CO
2
, have been observed at 15 K. Interestingly, sodium does not form a carbonite. Due to the lone pair on the carbon atom, salts of the carbonite ion would be protonated to form formate and formic acid, rather than the carbene.

<span class="mw-page-title-main">Diethynylbenzene dianion</span> Group of isomeric chemical compounds which are strong bases

In organic chemistry, a diethynylbenzene dianion is an anion consisting of two ethynyl anions as substituents on a benzene ring. With the chemical formula C
6
H
4
C2−
4
, three positional isomers are possible, differing in the relative positions of the two substituents around the ring:

The borate oxalates are chemical compounds containing borate and oxalate anions. Where the oxalate group is bound to the borate via oxygen, a more condensed anion is formed that balances less cations. These can be termed boro-oxalates, bis(oxalato)borates, or oxalatoborates or oxalate borates. The oxalatoborates are heterocyclic compounds with a ring containing -O-B-O-. Bis(oxalato)borates are spiro compounds with rings joined at the boron atom.

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

Lithium naphthalene is an organic salt with the chemical formula Li+[C10H8]. In the research laboratory, it is used as a reductant in the synthesis of organic, organometallic, and inorganic chemistry. It is usually generated in situ. Lithium naphthalene crystallizes with ligands bound to Li+.

<span class="mw-page-title-main">Superelectrophilic anion</span> Superelectrophilic anions

Superelectrophilic anions are a class of molecular ions that exhibit highly electrophilic reaction behavior despite their overall negative charge. Thus, they are even able to bind the unreactive noble gases or molecular nitrogen at room temperature. The only representatives known so far are the fragment ions of the type [B12X11] derived from the closo-dodecaborate dianions [B12X12]2–. X represents a substituent connected to a boron atom (cf. Fig. 1). For this reason, the following article deals exclusively with superelectrophilic anions of this type.

References

  1. "Lithium oxide anion". webbook.nist.gov.
  2. Poad, Berwyck L. J.; Reed, Nicholas D.; Hansen, Christopher S.; Trevitt, Adam J.; Blanksby, Stephen J.; Mackay, Emily G.; Sherburn, Michael S.; Chan, Bun; Radom, Leo (2016). "Preparation of an ion with the highest calculated proton affinity: ortho-diethynylbenzene dianion". Chemical Science. 7 (9): 6245–6250. doi: 10.1039/C6SC01726F . PMC   6024202 . PMID   30034765.
  3. Srivastava, Ambrish Kumar; Misra, Neeraj (6 February 2016). "OLi3O anion: Designing the strongest base to date using OLi3 superalkali". Chemical Physics Letters. 648: 152–155. Bibcode:2016CPL...648..152S. doi:10.1016/j.cplett.2016.02.010.
  4. Tian, Zhixin; Chan, Bun; Sullivan, Michael B.; Radom, Leo; Kass, Steven R. (2008-06-03). "Lithium monoxide anion: A ground-state triplet with the strongest base to date". Proceedings of the National Academy of Sciences of the United States of America. 105 (22): 7647–7651. Bibcode:2008PNAS..105.7647T. doi: 10.1073/pnas.0801393105 . ISSN   0027-8424. PMC   2409378 . PMID   18511563.

See also