inorganic nomenclature An inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds⁠that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemistry''. Inorga ...

, a manganate is any negatively charged

molecular entity In chemistry and physics, a molecular entity, or chemical entity, is "any constitutionally or isotopically distinct atom, molecule, ion, ion pair, radical, radical ion, complex, conformer, etc., identifiable as a separately distinguishable en ...

with

manganese Manganese is a chemical element; it has Symbol (chemistry), symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese was first isolated in the 1770s. It is a transition m ...

as the central atom.. However, the name is usually used to refer to the tetraoxidomanganate(2−) anion, MnO, also known as manganate(VI) because it contains manganese in the +6

oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical Electrical charge, charge of an atom if all of its Chemical bond, bonds to other atoms are fully Ionic bond, ionic. It describes the degree of oxidation (loss of electrons ...

. Manganates are the only known manganese(VI) compounds.. Other manganates include hypomanganate or manganate(V), , permanganate or manganate(VII), , and the dimanganate or dimanganate(III) . A manganate(IV) anion has been prepared by

radiolysis Radiolysis is the dissociation of molecules by ionizing radiation. It is the cleavage of one or several chemical bonds resulting from exposure to high-energy flux. The radiation in this context is associated with ionizing radiation; radiolysis is ...

of dilute solutions of permanganate.. It is mononuclear in dilute solution, and shows a strong absorption in the ultraviolet and a weaker absorption at 650 nm.

Structure

The manganate(VI) ion is tetrahedral, similar to sulfate or chromate: indeed, manganates are often isostructural with sulfates and chromates, a fact first noted by Eilhard Mitscherlich in 1831.. The

–

oxygen Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...

distance is 165.9 pm, about 3 pm longer than in permanganate. As a d¹ ion, it is paramagnetic, but any Jahn–Teller distortion is too small to be detected by

X-ray crystallography X-ray crystallography is the experimental science of determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to Diffraction, diffract in specific directions. By measuring th ...

. Manganates are dark green in colour, with a visible absorption maximum of ''λ''_max = 606 nm (''ε'' = ). The Raman spectrum has also been reported.

Preparation

Sodium Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...

and potassium manganates are usually prepared in the laboratory by stirring the equivalent permanganate in a concentrated solution (5–10 M) of the

hydroxide Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It ...

for 24 hours or with heating. : + → + + O₂ Potassium manganate is prepared industrially, as an intermediate to potassium permanganate, by dissolving manganese dioxide in molten

potassium hydroxide Potassium hydroxide is an inorganic compound with the formula K OH, and is commonly called caustic potash. Along with sodium hydroxide (NaOH), KOH is a prototypical strong base. It has many industrial and niche applications, most of which utili ...

with

potassium nitrate Potassium nitrate is a chemical compound with a sharp, salty, bitter taste and the chemical formula . It is a potassium salt of nitric acid. This salt consists of potassium cations and nitrate anions , and is therefore an alkali metal nit ...

or air as the

oxidizing agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or " accepts"/"receives" an electron from a (called the , , or ''electron donor''). In ot ...

. : + + O₂ → +

Disproportionation

Manganates are unstable towards disproportionation in all but the most alkaline of

aqueous solution An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, also known as sodium chloride (NaCl), in water ...

s. The ultimate products are permanganate and manganese dioxide, but the kinetics are complex and the mechanism may involve protonated and/or manganese(V) species..

Uses

Manganates, particularly the insoluble barium manganate, BaMnO₄, have been used as

s in

organic synthesis Organic synthesis is a branch of chemical synthesis concerned with the construction of organic compounds. Organic compounds are molecules consisting of combinations of covalently-linked hydrogen, carbon, oxygen, and nitrogen atoms. Within the gen ...

: they will oxidize primary

alcohol Alcohol may refer to: Common uses * Alcohol (chemistry), a class of compounds * Ethanol, one of several alcohols, commonly known as alcohol in everyday life ** Alcohol (drug), intoxicant found in alcoholic beverages ** Alcoholic beverage, an alco ...

s to

aldehyde In organic chemistry, an aldehyde () (lat. ''al''cohol ''dehyd''rogenatum, dehydrogenated alcohol) is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred ...

s and then to

carboxylic acid In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an Substituent, R-group. The general formula of a carboxylic acid is often written as or , sometimes as with R referring to an organyl ...

s, and secondary alcohols to

ketone In organic chemistry, a ketone is an organic compound with the structure , where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group (a carbon-oxygen double bond C=O). The simplest ketone is acetone ( ...

s. Barium manganate has also been used to oxidize

hydrazone Hydrazones are a class of organic compounds with the structure . They are related to ketones and aldehydes by the replacement of the oxygen =O with the = functional group. They are formed usually by the action of hydrazine on ketones or aldehydes. ...

s to diazo compounds.

Related compounds

Manganate is formally the

conjugate base A conjugate acid, within the Brønsted–Lowry acid–base theory, is a chemical compound formed when an acid gives a proton () to a base—in other words, it is a base with a hydrogen ion added to it, as it loses a hydrogen ion in the reve ...

of hypothetical manganic acid , which cannot be formed because of its rapid disproportionation. However, its second

acid dissociation constant In chemistry, an acid dissociation constant (also known as acidity constant, or acid-ionization constant; denoted ) is a quantitative property, quantitative measure of the acid strength, strength of an acid in Solution (chemistry), solution. I ...

has been estimated by pulse radiolysis techniques: :HMnO MnO + H⁺ p''K''_a = 7.4 ± 0.1

Manganites

The name " manganite" is used for compounds formerly believed to contain the anion , with manganese in the +3 oxidation state. However, most of these "manganites" do not contain discrete oxyanions, but are mixed oxides with perovskite (LaMn^IIIO₃, CaMn^IVO₃),

spinel Spinel () is the magnesium/aluminium member of the larger spinel group of minerals. It has the formula in the cubic crystal system. Its name comes from the Latin word , a diminutive form of ''spine,'' in reference to its pointed crystals. Prop ...

(LiMnO₄) or

sodium chloride Sodium chloride , commonly known as Salt#Edible salt, edible salt, is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. It is transparent or translucent, brittle, hygroscopic, and occurs a ...

(LiMn^IIIO₂, NaMn^IIIO₂) structures. One exception is potassium dimanganate(III), K₆Mn₂O₆, which contains discrete Mn₂O anions..

References

{{reflist, 30em Transition metal oxyanions Oxometallates