Perrhenic acid explained

Perrhenic acid is the chemical compound with the formula . It is obtained by evaporating aqueous solutions of . Conventionally, perrhenic acid is considered to have the formula, and a species of this formula forms when rhenium(VII) oxide sublimes in the presence of water or steam.^[1] When a solution of is kept for a period of months, it breaks down and crystals of are formed, which contain tetrahedral . For most purposes, perrhenic acid and rhenium(VII) oxide are used interchangeably. Rhenium can be dissolved in nitric or concentrated sulfuric acid to produce perrhenic acid.

Properties

The structure of solid perrhenic acid is .^[2] This species is a rare example of a metal oxide coordinated to water; most often metal–oxo–aquo species are unstable with respect to their corresponding hydroxides:

The two rhenium atoms have different bonding geometries, with one being tetrahedral and the other octahedral, and with the water ligands coordinated to the latter.

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

Reactions

Perrhenic acid or the related anhydrous oxide converts to dirhenium heptasulfide upon treatment with hydrogen sulfide:

The heptasulfide catalyzes various reductions.^[3]

Perrhenic acid in the presence of hydrochloric acid undergoes reduction in the presence of thioethers and tertiary phosphines to give rhenium(V) complexes with the formula .^[4]

Perrhenic acid combined with platinum on a support gives rise to a useful hydrogenation and hydrocracking catalyst for the petroleum industry.^[5] For example, silica impregnated with a solution of perrhenic acid is reduced with hydrogen at 500 °C. This catalyst is used in the dehydrogenation of alcohols and also promotes the decomposition of ammonia.

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 alkenes with hydrogen peroxide.^[6] Perrhenic acid catalyses the dehydration of oximes to nitriles.^[7]

Other uses

Perrhenic acid is also used in the manufacture of x-ray targets.^{[8] [9]}

See also

• Perrhenate
• Rhenium(VII) oxide

Notes and References

1. Glemser, O. . Müller, A. . Schwarzkopf, H. . Gasförmige Hydroxide. IX. Über ein Gasförmiges Hydroxid des Rheniums . . 1964 . 334 . 1–2 . 21–26. German . 10.1002/zaac.19643340105. .
2. Beyer, H.; Glemser, O.; Krebs, B. "Dirhenium Dihydratoheptoxide – New Type of Water Bonding in an Aquoxide" Angewandte Chemie, International Edition English 1968, Volume 7, Pages 295 - 296. .
3. Schwarz, D. E. . Frenkel, A. I. . Nuzzo, R. G. . Rauchfuss, T. B. . Vairavamurthy, A. . Electrosynthesis of . XAS Analysis of,, and . Chemistry of Materials . 2004 . 16 . 151–158 . 10.1021/cm034467v.
4. Book: Phosphine Complexes of Rhenium . Parshall, G. W. . . 1997 . 17 . 110 - 112. 10.1002/9780470132487.ch31 . Shive . L. W. . Cotton . F. A.. 9780470132487 .
5. Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. .
6. van Vliet, M. C. A. . Arends, I. W. C. E. . Roger A. Sheldon . Sheldon, R. A. . 1999. Rhenium Catalysed Epoxidations with Hydrogen Peroxide: Tertiary Arsines as Effective Cocatalysts. J. Chem. Soc., Perkin Trans. 1. 377–80 . 10.1039/a907975k. 3 .
7. Ishihara, K. . Furuya, Y. . Yamamoto, H. . Rhenium(VII) Oxo Complexes as Extremely Active Catalysts in the Dehydration of Primary Amides and Aldoximes to Nitriles . . 41 . 2983–2986 . 2002 . 10.1002/1521-3773(20020816)41:16<2983::AID-ANIE2983>3.0.CO;2-X . 16 . 12203432 .
8. http://www.gehealthcare.com/usen/service/time_material_support/docs/Radplus2100.pdf{{dead link|date=March 2018 |bot=InternetArchiveBot |fix-attempted=yes }}
9. [X-ray#Sources]