Perrhenic acid
Encyclopedia
Perrhenic acid is the chemical compound
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements that can be separated into simpler substances by chemical reactions. Chemical compounds have a unique and defined chemical structure; they consist of a fixed ratio of atoms that are held together...

 with the formula Re2O7(OH2)2. It is obtained by evaporating aqueous solutions of Re2O7. Conventionally, perrhenic acid is considered to have the formula HReO4, and a species of this formula forms when rhenium(VII) oxide sublimes in the presence of water or steam. When a solution of Re2O7 is kept for a period of months, it breaks down and crystals of HReO4.H2O are formed, which contain tetrahedral ReO4 For most purposes, perrhenic acid and rhenium(VII) oxide
Rhenium(VII) oxide
Rhenium oxide is the chemical compound with the formula Re2O7. It is the anhydride of the hypothetical acid . Perrhenic acid, Re2O7·2H2O, however is closely related structurally to Re2O7. Solid Re2O7 is polymeric consisting, unusually, of the metal centers in two coordination environments...

 are used interchangeably. Rhenium can be dissolved in nitric
Nitric acid
Nitric acid , also known as aqua fortis and spirit of nitre, is a highly corrosive and toxic strong acid.Colorless when pure, older samples tend to acquire a yellow cast due to the accumulation of oxides of nitrogen. If the solution contains more than 86% nitric acid, it is referred to as fuming...

 or concentrated sulfuric acid
Sulfuric acid
Sulfuric acid is a strong mineral acid with the molecular formula . Its historical name is oil of vitriol. Pure sulfuric acid is a highly corrosive, colorless, viscous liquid. The salts of sulfuric acid are called sulfates...

 to produce perrhenic acid.

Properties

The structure of solid perrhenic acid is [O3Re-O-ReO3(H2O)2]. This species is a rare example of a metal oxide
Oxide
An oxide is a chemical compound that contains at least one oxygen atom in its chemical formula. Metal oxides typically contain an anion of oxygen in the oxidation state of −2....

 coordinated to water
Water
Water is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...

 - most often metal-oxo-aquo species are unstable with respect to the corresponding hydroxide
Hydroxide
Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and a hydrogen atom held together by a covalent bond, and carrying a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, as a ligand, a nucleophile, and a...

s:
M(O)(H2O) → M(OH)2

Gaseous perrhenic acid is tetrahedral, as suggested by its formula HReO4.

Reactions

Perrhenic acid or the related anhydrous oxide Re2O7 converts to dirhenium heptasulfide upon treatment with hydrogen sulfide
Hydrogen sulfide
Hydrogen sulfide is the chemical compound with the formula . It is a colorless, very poisonous, flammable gas with the characteristic foul odor of expired eggs perceptible at concentrations as low as 0.00047 parts per million...

:
Re2O7+ 7 H2S → Re2S7 + 7 H2O

The heptasulfide, which has a complex structure, catalyses the hydrogenation of double bonds and is useful because it tolerates sulfur compounds, which poison noble metal catalysts. Re2S7 also catalyses the reduction of nitric oxide to N2O.

Perrhenic acid in the presence of HCl undergoes reduction in the presence of thioether
Thioether
A thioether is a functional group in organosulfur chemistry with the connectivity C-S-C as shown on right. Like many other sulfur-containing compounds, volatile thioethers have foul odors. A thioether is similar to an ether except that it contains a sulfur atom in place of the oxygen...

s and tertiary phosphine
Triphenylphosphine
Triphenylphosphine is a common organophosphorus compound with the formula P3 - often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists as relatively air stable, colorless crystals at room temperature...

s to give Re(V) complexes with the formula ReOCl3L2.

Perrhenic acid combined with platinum
Platinum
Platinum is a chemical element with the chemical symbol Pt and an atomic number of 78. Its name is derived from the Spanish term platina del Pinto, which is literally translated into "little silver of the Pinto River." It is a dense, malleable, ductile, precious, gray-white transition metal...

 on a support gives rise to a useful hydrogenation
Hydrogenation
Hydrogenation, to treat with hydrogen, also a form of chemical reduction, is a chemical reaction between molecular hydrogen and another compound or element, usually in the presence of a catalyst. The process is commonly employed to reduce or saturate organic compounds. Hydrogenation typically...

 and hydrocracking catalyst for the petroleum industry
Petroleum industry
The petroleum industry includes the global processes of exploration, extraction, refining, transporting , and marketing petroleum products. The largest volume products of the industry are fuel oil and gasoline...

. For example, silica impregnated with a solution of perrhenic acid is reduced with hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...

 at 500 °C. This catalyst is used in the dehydrogenation
Dehydrogenation
Dehydrogenation is a chemical reaction that involves the elimination of hydrogen . It is the reverse process of hydrogenation. Dehydrogenation reactions may be either large scale industrial processes or smaller scale laboratory procedures....

 of alcohol
Alcohol
In chemistry, an alcohol is an organic compound in which the hydroxy functional group is bound to a carbon atom. In particular, this carbon center should be saturated, having single bonds to three other atoms....

s and also promotes the decomposition of ammonia
Ammonia
Ammonia is a compound of nitrogen and hydrogen with the formula . It is a colourless gas with a characteristic pungent odour. Ammonia contributes significantly to the nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers. Ammonia, either directly or...

.

Catalysis

Perrhenic acid is a precursor to a variety of homogeneous catalysts, some of which are promising in niche applications that can justify the high cost of rhenium. In combination with tertiary arsines, perrhenic acid gives a catalyst for the epoxidation of alkene
Alkene
In organic chemistry, an alkene, olefin, or olefine is an unsaturated chemical compound containing at least one carbon-to-carbon double bond...

s with hydrogen peroxide
Hydrogen peroxide
Hydrogen peroxide is the simplest peroxide and an oxidizer. Hydrogen peroxide is a clear liquid, slightly more viscous than water. In dilute solution, it appears colorless. With its oxidizing properties, hydrogen peroxide is often used as a bleach or cleaning agent...

. Perrhenic acid catalyses the dehydration of oxime
Oxime
An oxime is a chemical compound belonging to the imines, with the general formula R1R2C=NOH, where R1 is an organic side chain and R2 may be hydrogen, forming an aldoxime, or another organic group, forming a ketoxime. O-substituted oximes form a closely related family of compounds...

s to nitrile
Nitrile
A nitrile is any organic compound that has a -C≡N functional group. The prefix cyano- is used interchangeably with the term nitrile in industrial literature. Nitriles are found in many useful compounds, one example being super glue .Inorganic compounds containing the -C≡N group are not called...

s.

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