Tetranitratoborate Explained

Tetranitratoborate is an anion composed of boron with four nitrate groups. It has formula . It can form salts with large cations such as tetramethylammonium nitratoborate,[1] or tetraethylammonium tetranitratoborate. The ion was first discovered by C. R. Guibert and M. D. Marshall in 1966 after failed attempts to make neutral (non-ionic) boron nitrate,, which has resisted attempts to make it; if it exists, it is unstable above −78 °C.

Other related ions are the slightly more stable tetraperchloratoborates, with perchlorate groups instead of nitrate, and tetranitratoaluminate[2] with the next atom down the periodic table, aluminium instead of boron .

Formation

Tetramethylammonium chloride reacts with to make . Then the tetrachloroborate is reacted with at around −20 °C to form tetramethylammonium nitratoborate, and other gases such as and .

Another mechanism to make tetranitratoborate salts is to shake a metal nitrate with in chloroform at 20 °C for several days. Trichloronitratoborate is an unstable intermediate.

[3]

Properties

The infrared spectrum of tetramethylammonium nitratoborate includes a prominent line at 1,612 cm−1 with shoulders at 1582 and 1,626 cm−1 attributed to v4. Also prominent is 1,297 and 1,311 cm−1 attributed to v1, with these vibrations due to the nitrate bonded via one oxygen.[1]

The density of tetramethylammonium nitratoborate is 1.555 g·cm−3. It is colourless and crystalline. As tetramethylammonium nitratoborate is heated it has some sort of transition between 51 and 62 °C. It decomposes above 75 °C producing gas. Above 112 °C it is exothermic, and a solid is left if it is heated to 160 °C.[4]

Tetramethylammonium nitratoborate is insoluble in cold water but slightly soluble in hot water. It does not react with water. It also dissolves in liquid ammonia, acetonitrile, methanol, and dimethylformamide.[1] It reacts with liquid sulfur dioxide.[1] [5]

At room temperature tetramethylammonium nitratoborate is stable for months. It does not explode with impact.[1]

Alkali metal tetranitratoborates are unstable at room temperature and decompose.[3]

1-Ethyl-3-methyl-imidazolimium tetranitratoborate was discovered in 2002. It is an ionic liquid that turns solid at −25 °C.[6]

Notes and References

  1. Guibert. C. R.. M. D. Marshall . 1966. Synthesis of the Tetranitratoborate Anion. Journal of the American Chemical Society. 88. 1. 189–190. 0002-7863. 10.1021/ja00953a051.
  2. Book: Jones, CJ Bigler. Transition and Main Group Metals Applied to Oxidative Functionalization of Methane and Use as High Oxygen Carriers for Rocket Propellants. 3 February 2014. 2007. 9780549231066. 139.
  3. Titova. K. V.. V. Ya. Rosolovskii . 1975. Reaction of nitrates of monovalent cations with BCl3. Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 24. 10. 2246–2248. 0568-5230. 10.1007/BF00929774.
  4. Titova. K. V.. V. Ya. Rosolovskii . 1970. Tetraalkylammonium nitratoborates. Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 19. 12. 2515–2519. 0568-5230. 10.1007/BF00854900.
  5. Book: C.C. Addison . D. Sutton . Progress in Inorganic Chemistry. 8. 216.
  6. Jones. C. Bigler. Ralf Haiges . Thorsten Schroer . Karl O. Christe . 2006. Oxygen-Balanced Energetic Ionic Liquid. Angewandte Chemie International Edition. 45. 30. 4981–4984. 1433-7851. 10.1002/anie.200600735 . 16819744. free.