Vanadyl nitrate explained

Vanadyl nitrate, also called vanadium oxytrinitrate or vanadium oxynitrate is an inorganic compound of vanadium in the +5 oxidation state with nitrate ligands and oxygen. The formula is VO(NO3)3. It is a pale yellow viscous liquid.[1]

Production

It is made by soaking vanadium pentoxide in liquid dinitrogen pentoxide for durations around two days at room temperature. The yield for this method is about 85%.

V2O5 + 3 N2O5 → 2 VO(NO3)3.Purification can be achieved by vacuum distillation.

Mononitratodioxovanadium (VO2NO3) is an intermediate in this synthesis. It is a brick red solid.[2] [3]

Vanadyl nitrate can also be made from vanadyl trichloride VOCl3 and dinitrogen pentoxide.[4]

Structure

VO(NO3)3 has a distorted pentagonal bipyramid shape with idealized Cs (mirror) symmetry. The vanadium oxygen bond (157.2 pm) is typical for vanadyl(V). Two nitrate groups in the pentagonal plane are bidentate (V-O distances range from 199 to 206 pm). The third nitrate spans the pentagonal plane (197 pm) to the position trans to oxo (223 pm).[5] [6]

Properties

Vanadyl nitrate dissolves in dichloromethane, nitromethane, carbon tetrachloride, and saturated hydrocarbons. 1-Hexene, or other unsaturated hydrocarbons ignite upon contact with vanadyl nitrate.[7] Upon contact with water, it irreversibly hydrolyzes, releasing nitric acid.[8] [9]

The ultraviolet spectrum of the liquid shows an absorption band peaking at 208 nm with a shoulder at 242 nm. At 55 °C the gaseous vanadyl nitrate has absorption bands also at 486, 582 and 658 nm in the visual light spectrum.[9] in the infrared region, liquid vanadyl nitrate absorbs at 1880, 1633, 1612, 1560, 1306, 1205, 1016, 996, 965, 895, 783, 632, 457, 357, 301, 283, 234, 193, 133, 93 and 59 cm−1.[9] Gaseous vanadyl nitrate has absorption bands at 775, 783, 786, 962.5, 994.4, 997.5, 1000.5, 1006.2, 1012, 1016.3, 1020, 1198, 1211, 1216.3, 1564, 1612, 1629, 1632, 1635, 1648 and 1888 cm−1.[1] Many of these bands are due to stretching in nitrogen–oxygen bonds, but 1016.3 cm−1 is due to the double vanadium–oxygen bond. 786 is due to out of phase wagging in N-O, and 775 is due to deformation in O-N=O in the mirror plane.[1]

Reactions

It is a nitrating agent for aromatic compounds. Reactions proceed at room temperature. Often dichloromethane is used as an inert solvent.[10] Nitrotoluene, methyl benzoate and benzoic acid are nitrated by prolonged exposure over a few days.[10] Benzonitrile does not react.[10] [11]

Vanadyl nitrate form a solid pale yellow adduct with boron trifluoride.[8] An adduct is also formed with acetonitrile.[10]

References

  1. Brandán. Silvia A.. C. Socolsky . Aida Ben Altabef . 2009. DFT Calculations of the Molecular Force Field of Vanadyl Nitrate, VO(NO3)3. Zeitschrift für anorganische und allgemeine Chemie. 635. 3. 582–592. 0044-2313. 10.1002/zaac.200801244. 11336/53374. free.
  2. Book: Cotton. F. Albert. Wilkinson. Geoffrey. Advanced Inorganic Chemistry A Comprehensive Text. 1966. John Wiley. 814. 5.
  3. Pantonin. John A.. Albert K. Fischer . Edward A. Heintz . 1960. The preparation of mononitratodioxovanadium(V), VO2NO3. Journal of Inorganic and Nuclear Chemistry. 14. 1–2. 145–147. 0022-1902. 10.1016/0022-1902(60)80220-5.
  4. Schmeisser. Martin. 1955. Die Chemie der anorganischen Acylnitrate (ein Problem des Nitrylchlorids) und Acylperchlorate (ein Problem des Dichlorhexoxyds). Angewandte Chemie. 67. 17–18. 493–501. 0044-8249. 10.1002/ange.19550671708. 1955AngCh..67..493S . de.
  5. Smart. Bruce A.. Heather E. Robertson . David W. H. Rankin . Eric G. Hope . Colin J. Marsden . 1999. What is the coordination number of vanadium in vanadyl nitrate, VO(NO3)3? A Study of its Molecular Structure in the Gas Phase by Electron Diffraction and ab initio calculations. Journal of the Chemical Society, Dalton Transactions. 3. 473–478. 0300-9246. 10.1039/A806710D. (free download)
  6. Book: Davidson, G.. Spectroscopic Properties of Inorganic and Organometallic Compounds. 30 September 2014. 2000-01-01. Royal Society of Chemistry. 9780854044269. 516–517.
  7. Book: Fedoroff. Basil T. Sheffield. Oliver E. Encyclopedia of Explosives and Related Items Vol 10 of 10- U to Z. 10. V4.
  8. Web site: AD296097 Experimental Studies of the Reactions of N2O5 with Metal Acid Anhydrides and BF3. Harris. Arlo D.. John C. Trebellas. 26 April 1962. Armed Services Technical Information Agency. 30 September 2014. Arlington Hall Station. https://web.archive.org/web/20150924123859/http://www.dtic.mil/get-tr-doc/pdf?AD=AD0296037. dead. September 24, 2015.
  9. Brandán. S.A.. A. Ben Altabef, E.L. Varetti. 1995. Vibrational and electronic spectra of vanadyl nitrate, VO(NO3)3. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 51. 4. 669–675. 1386-1425. 10.1016/0584-8539(94)00154-4. 1995AcSpA..51..669B. Varetti. E. L..
  10. Dove. Michael F. A.. Berthold Manz . John Montgomery . Gerald Pattenden . Simon A. Wood . 1998. Vanadium(V) Oxytrinitrate, VO(NO3)3. A Powerful Reagent for the Nitration of Aromatic Compounds at Room Temperature under Non-Acidic Conditions. Journal of the Chemical Society, Perkin Transactions 1. 10. 1589–1590. 0300-922X. 10.1039/A801771I.
  11. Book: Aitken. R. Alan. Alajarin. Mateo. Allen. D. W. . Mikael Begtrup . Daniel Bellus . J. Berna-Canovas . H. Boeckemeier . Stefan Bräse . I.R. Butler . Jose Chiara . Henri-J. Cristau . I. Gorrell . D. Keck . Terence Kee . Carmen Lopez-Leonardo . T. Muller . Patrick J. Murphy . Patrick O'Leary . Beate Priewisch . L.K. Rasmussen . Karola Rück-Braun . Bjoern Schlummer . Andreas Schmidt . Paul James Stevenson . J.C. Tebby . David Virieux. Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 31b: Arene-X (X=N, P). 29 September 2014. 2014-05-14. Georg Thieme Verlag. 9783131720719. 1215.

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