Tetranitratoborate

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Boron nitrate redirects here. For the coating material used in casting, see Boron nitride.

Tetranitratoborate is an anion composed of boron with four nitrate groups. It can form salts with large cations such as tetramethyl ammonium nitratoborate,[1] or tetraethyl ammonium tetranitratoborate.[2]

The ion was first discovered by C. R. Guibert, M. D. Marshall in 1966 after failed attempts to make boron nitrate.[1]

The related molecule, boron nitrate B(NO3)3, has resisted attempts to make it, and if it exists it is unstable above -78 °C.[2] Despite this non-existence it has a CAS number of 71816-39-2 and ChemSpider number of 25934735.

Other related ions are the slightly more stable tetraperchloratoborates, with perchlorate groups instead of nitrate, and tetranitratoaluminate[3] with the next atom down the periodic table, aluminium instead of boron ([Al(NO)4]).

Formation[edit]

Tetramethyl ammonium chloride reacts with BCl3 to make (CH3)4NBCl4. Then the tetrachloroborate is reacted with N2O4 at around -20° to form tetramethyl ammonium nitratoborate, and other gases such as NO2Cl and Cl2.[2]

Another mechanism to make tetranitratoborate salts is to shake a metal nitrate with BCl3 in chloroform at 20 °C for several days. Chloronitratoborate [Cl3BNO3] is an unstable intermediate.

MNO3 + BCl3 M[Cl3BNO3]
4M[Cl3BNO3] 3M[BCl4] + MB(NO3)4][4]

Properties[edit]

The infrared spectrum of tetramethyl ammonium nitratoborate includes a prominent line at 1612 cm−1 with shoulders at 1582 and 1626 cm−1 attributed to v4. Also prominent is 1297 and 1311 cm−1 attributed to v1, with these vibrations due to the nitrate bonded via one oxygen.[1]

The density of tetramethyl ammonium nitratoborate is 1.555. It is colourless and crystalline. As tetramethyl ammonium nitratoborate is heated it has some sort of transition between 51 °C and 62°. It decomposes above 75 °C producing gas. Above 112° it is exothermic, and a solid is left if it is heated to 160 °C.[2]

Tetramethyl ammonium 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 tetramethyl ammonium nitratoborate is stable for months. It does not explode with impact.[1]

Alkali metal tetranitratoborates are unstable at room temperature and decompose.[4]

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

References[edit]

  1. ^ a b c d e f Guibert, C. R.; M. D. Marshall (1966). "Synthesis of the Tetranitratoborate Anion". Journal of the American Chemical Society 88 (1): 189–190. doi:10.1021/ja00953a051. ISSN 0002-7863. 
  2. ^ a b c d 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. doi:10.1007/BF00854900. ISSN 0568-5230. 
  3. ^ Jones, CJ Bigler (2007). Transition and Main Group Metals Applied to Oxidative Functionalization of Methane and Use as High Oxygen Carriers for Rocket Propellants. ProQuest. p. 139. ISBN 9780549231066. Retrieved 3 February 2014. 
  4. ^ a b 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. doi:10.1007/BF00929774. ISSN 0568-5230. 
  5. ^ C.C. Addison and D. Sutton. Progress in Inorganic Chemistry 8. p. 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. doi:10.1002/anie.200600735. ISSN 1433-7851.