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| CASNo_Ref = {{cascite|unchecked|??}}
| CASNo_Ref = {{cascite|unchecked|??}}
| CASNo = 16017-37-1
| CASNo = 16017-37-1
| PubChem = <!--140021 has erroneous hydrogen due to V in oxidation state 2-->
| PubChem = 135096579
| ChemSpiderID = 67496691
| ChemSpiderID = 67496691
| ChemSpiderID_Ref = {{chemspidercite|changedt|chemspider}}
| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
| InChI =1S/3NO3.O.V/c3*2-1(3)4;;/q3*-1;;+3
| InChI =1S/3NO3.O.V/c3*2-1(3)4;;/q3*-1;;+3
| InChIKey =NRKQBMOGOKEWPX-UHFFFAOYSA-N
| InChIKey =NRKQBMOGOKEWPX-UHFFFAOYSA-N
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| BoilingPtC = 86 to 91
| BoilingPtC = 86 to 91
| BoilingPt_notes = at 0.7mm Hg
| BoilingPt_notes = at 0.7mm Hg
| Solubility = water
| Solubility = Hydrolysis
}}
}}
|Section3={{Chembox Hazards
|Section3={{Chembox Hazards
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}}
}}
|Section8={{Chembox Related
|Section8={{Chembox Related
| OtherCompounds = [[niobium nitrate]], [[vanadyl perchlorate]]
| OtherCompounds = [[titanium nitrate]], [[vanadyl perchlorate]]
}}
}}
}}
}}
'''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(NO<sub>3</sub>)<sub>3</sub>. It is a pale yellow viscous liquid.<ref name="Brandán2009">{{cite journal|last=Brandán|first=Silvia A.|author2=C. Socolsky |author3=Aida Ben Altabef |year=2009|title=DFT Calculations of the Molecular Force Field of Vanadyl Nitrate, VO(NO3)3|journal=Zeitschrift für anorganische und allgemeine Chemie|volume=635|issue=3|pages=582–592|issn=0044-2313|doi=10.1002/zaac.200801244}}</ref>
'''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(NO<sub>3</sub>)<sub>3</sub>. It is a pale yellow viscous liquid.<ref name="Brandán2009">{{cite journal|last=Brandán|first=Silvia A.|author2=C. Socolsky |author3=Aida Ben Altabef |year=2009|title=DFT Calculations of the Molecular Force Field of Vanadyl Nitrate, VO(NO<sub>3</sub>)<sub>3</sub>|journal=Zeitschrift für anorganische und allgemeine Chemie|volume=635|issue=3|pages=582–592|issn=0044-2313|doi=10.1002/zaac.200801244|hdl=11336/53374|hdl-access=free}}</ref>

==Production==
==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%.<ref name="Harris62"/>
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%.<ref name="Harris62"/>
:V<sub>2</sub>O<sub>5</sub> + 3&nbsp;N<sub>2</sub>O<sub>5</sub> → 2&nbsp;VO(NO<sub>3</sub>)<sub>3</sub>.
:V<sub>2</sub>O<sub>5</sub> + 3&nbsp;N<sub>2</sub>O<sub>5</sub> → 2&nbsp;VO(NO<sub>3</sub>)<sub>3</sub>.
⚫
Purification can be achieved by vacuum distillation.<ref name="Harris62"/>


⚫
Mononitratodioxovanadium (VO<sub>2</sub>NO<sub>3</sub>) is an intermediate in this synthesis. It is a brick red solid.<ref>{{cite book|last1=Cotton|first1=F. Albert|last2=Wilkinson|first2=Geoffrey|title=Advanced Inorganic Chemistry A Comprehensive Text|year=1966|publisher=John Wiley|page=814|edition=5}}</ref><ref name="Pantonin1960">{{cite journal|last=Pantonin|first=John A.|author2=Albert K. Fischer |author3=Edward A. Heintz |year=1960|title=The preparation of mononitratodioxovanadium(V), VO<sub>2</sub>NO<sub>3</sub>|journal=Journal of Inorganic and Nuclear Chemistry|volume=14|issue=1–2|pages=145–147|issn=0022-1902|doi=10.1016/0022-1902(60)80220-5}}</ref>
⚫
Purification can be done by vacuum distillation.<ref name="Harris62"/>


Vanadyl nitrate can also be made from vanadyl trichloride VOCl<sub>3</sub> and dinitrogen pentoxide.<ref name="Schmeisser1955">{{cite journal|last=Schmeisser|first=Martin|year=1955|title=Die Chemie der anorganischen Acylnitrate (ein Problem des Nitrylchlorids) und Acylperchlorate (ein Problem des Dichlorhexoxyds)|journal=Angewandte Chemie|volume=67|issue=17–18|pages=493–501|issn=0044-8249|doi=10.1002/ange.19550671708|language=de}}</ref>
Vanadyl nitrate can also be made from vanadyl trichloride VOCl<sub>3</sub> and dinitrogen pentoxide.<ref name="Schmeisser1955">{{cite journal|last=Schmeisser|first=Martin|year=1955|title=Die Chemie der anorganischen Acylnitrate (ein Problem des Nitrylchlorids) und Acylperchlorate (ein Problem des Dichlorhexoxyds)|journal=Angewandte Chemie|volume=67|issue=17–18|pages=493–501|issn=0044-8249|doi=10.1002/ange.19550671708|bibcode=1955AngCh..67..493S |language=de}}</ref>


==Structure==
==Structure==
VO(NO<sub>3</sub>)<sub>3</sub> has a distorted pentagonal bipyramid shape with idealized C<sub>s</sub> (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).<ref name="Smart1999">{{cite journal|last=Smart|first=Bruce A.|author2=Heather E. Robertson |author3=David W. H. Rankin |author4=Eric G. Hope |author5=Colin J. Marsden |year=1999|title=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=Journal of the Chemical Society, Dalton Transactions|issue=3|pages=473–478|issn=0300-9246|doi=10.1039/A806710D}} (free download)</ref><ref name="Davidson2000">{{cite book|last=Davidson|first=G.|title=Spectroscopic Properties of Inorganic and Organometallic Compounds|url=https://books.google.com/books?id=SzfKOHmyoLsC&pg=PA516|access-date=30 September 2014|date=2000-01-01|publisher=Royal Society of Chemistry|isbn=9780854044269|pages=516–517}}</ref>
VO(NO<sub>3</sub>)<sub>3</sub> has a distorted pentagonal bipyramid shape with idealized C<sub>s</sub> (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).<ref name="Smart1999">{{cite journal|last=Smart|first=Bruce A.|author2=Heather E. Robertson |author3=David W. H. Rankin |author4=Eric G. Hope |author5=Colin J. Marsden |year=1999|title=What is the coordination number of vanadium in vanadyl nitrate, VO(NO<sub>3</sub>)<sub>3</sub>? A Study of its Molecular Structure in the Gas Phase by Electron Diffraction and ab initio calculations|journal=Journal of the Chemical Society, Dalton Transactions|issue=3|pages=473–478|issn=0300-9246|doi=10.1039/A806710D}} (free download)</ref><ref name="Davidson2000">{{cite book|last=Davidson|first=G.|title=Spectroscopic Properties of Inorganic and Organometallic Compounds|url=https://books.google.com/books?id=SzfKOHmyoLsC&pg=PA516|access-date=30 September 2014|date=2000-01-01|publisher=Royal Society of Chemistry|isbn=9780854044269|pages=516–517}}</ref>


==Properties==
==Properties==
Vanadyl nitrate dissolves in water, but decomposes.<ref name="Harris62">{{cite web|title=AD296097 Experimental Studies of the Reactions of N2O5 with Metal Acid Anhydrides and BF3|last=Harris|first=Arlo D.|author2=John C. Trebellas|date=26 April 1962|publisher=Armed Services Technical Information Agency|access-date=30 September 2014|location=Arlington Hall Station|url=http://www.dtic.mil/get-tr-doc/pdf?AD=AD0296037}}</ref> Nitric acid is formed as a result of the reaction with water.<ref name=Varetti>{{cite journal|last=Brandán|first=S.A.|author2=A. Ben Altabef, E.L. Varetti|year=1995|title=Vibrational and electronic spectra of vanadyl nitrate, VO(NO3)3|journal=Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy|volume=51|issue=4|pages=669–675|issn=1386-1425|doi=10.1016/0584-8539(94)00154-4|bibcode=1995AcSpA..51..669B|last3=Varetti|first3=E. L.}}</ref>
Vanadyl nitrate dissolves in dichloromethane, nitromethane, carbon tetrachloride, and saturated hydrocarbons.<ref name="Dove1998"/> 1-Hexene, or other unsaturated hydrocarbons ignite upon contact with vanadyl nitrate.<ref name="Harris62"/><ref name=fed10>{{cite book|last1=Fedoroff|first1=Basil T|last2=Sheffield|first2=Oliver E|title=Encyclopedia of Explosives and Related Items Vol 10 of 10- U to Z|volume=10|page=V4|url=https://html1-f.scribdassets.com/5n1zz8vvr4sm3p8/images/136-c19277b6e3.jpg}}{{Dead link|date=April 2024 |bot=InternetArchiveBot |fix-attempted=yes }}</ref> Upon contact with water, it irreversibly hydrolyzes, releasing [[nitric acid]].<ref name="Harris62">{{cite web|title=AD296097 Experimental Studies of the Reactions of N2O5 with Metal Acid Anhydrides and BF3|last=Harris|first=Arlo D.|author2=John C. Trebellas|date=26 April 1962|publisher=Armed Services Technical Information Agency|access-date=30 September 2014|location=Arlington Hall Station|url=http://www.dtic.mil/get-tr-doc/pdf?AD=AD0296037|archive-url=https://web.archive.org/web/20150924123859/http://www.dtic.mil/get-tr-doc/pdf?AD=AD0296037|url-status=dead|archive-date=September 24, 2015}}</ref><ref name=Varetti>{{cite journal|last=Brandán|first=S.A.|author2=A. Ben Altabef, E.L. Varetti|year=1995|title=Vibrational and electronic spectra of vanadyl nitrate, VO(NO<sub>3</sub>)<sub>3</sub>|journal=Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy|volume=51|issue=4|pages=669–675|issn=1386-1425|doi=10.1016/0584-8539(94)00154-4|bibcode=1995AcSpA..51..669B|last3=Varetti|first3=E. L.}}</ref>


⚫
The ultraviolet spectrum of the liquid shows an absorption band peaking at 208&nbsp;nm with a shoulder at 242&nbsp;nm. At 55&nbsp;°C the gaseous vanadyl nitrate has absorption bands also at 486, 582 and 658&nbsp;nm in the visual light spectrum.<ref name=Varetti/> 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&nbsp;cm<sup>−1</sup>.<ref name=Varetti/> 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&nbsp;cm<sup>−1</sup>.<ref name="Brandán2009"/> Many of these bands are due to stretching in nitrogen–oxygen bonds, but 1016.3&nbsp;cm<sup>−1</sup> 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.<ref name="Brandán2009"/>
Solvents include dichloromethane, nitromethane, carbon tetrachloride, cyclohexane, trichlorofluoromethane. It is probably incompatible with amines, aromatic hydrocarbons, and ethers.<ref name="Dove1998"/>

Vanadyl nitrate is stable under nitrogen,<ref name="Dove1998"/> ozone or oxygen.<ref name="Harris62"/> The liquid is indefinitely stable at room temperature, unlike some other transition metal nitrates that decompose to nitrogen oxides.<ref name="Harris62"/> Over 80&nbsp;°C it decomposes slowly.<ref name="Harris62"/>


==Reactions==
==Reactions==
It is a nitrating agent, adding nitro groups to aromatic compounds such as benzene, phenol, chlorobenzene, anisole, acetanilide, benzoic acid, ethyl benzoate, and toluene.<ref name="AitkenAlajarin2014">{{cite book|last1=Aitken|first1=R. Alan|last2=Alajarin|first2=Mateo|last3=Allen|first3=D. W. |author4=Mikael Begtrup |author5=Daniel Bellus |author6=J. Berna-Canovas |author7=H. Boeckemeier |author8=Stefan Bräse |author9=I.R. Butler |author10=Jose Chiara |author11=Henri-J. Cristau |author12=I. Gorrell |author13=D. Keck |author14=Terence Kee |author15=Carmen Lopez-Leonardo |author16=T. Muller |author17=Patrick J. Murphy |author18=Patrick O'Leary |author19=Beate Priewisch |author20=L.K. Rasmussen |author21=Karola Rück-Braun |author22=Bjoern Schlummer |author23=Andreas Schmidt |author24=Paul James Stevenson |author25=J.C. Tebby |author26=David Virieux|title=Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 31b: Arene-X (X=N, P)|url=https://books.google.com/books?id=eiGGAwAAQBAJ&pg=PA1215|access-date=29 September 2014|date=2014-05-14|publisher=Georg Thieme Verlag|isbn=9783131720719|page=1215}}</ref>
It is a [[nitration|nitrating agent]] for aromatic compounds. Reactions proceed at room temperature. Often dichloromethane is used as an inert solvent.<ref name="Dove1998">{{cite journal|last=Dove|first=Michael F. A.|author2=Berthold Manz |author3=John Montgomery |author4=Gerald Pattenden |author5=Simon A. Wood |year=1998|title=Vanadium(V) Oxytrinitrate, VO(NO<sub>3</sub>)<sub>3</sub>. A Powerful Reagent for the Nitration of Aromatic Compounds at Room Temperature under Non-Acidic Conditions|journal=Journal of the Chemical Society, Perkin Transactions 1|issue=10|pages=1589–1590|issn=0300-922X|doi=10.1039/A801771I}}</ref> Nitrotoluene, [[methyl benzoate]] and [[benzoic acid]] are nitrated by prolonged exposure over a few days.<ref name="Dove1998"/> Benzonitrile does not react.<ref name="Dove1998"/> <ref name="AitkenAlajarin2014">{{cite book|last1=Aitken|first1=R. Alan|last2=Alajarin|first2=Mateo|last3=Allen|first3=D. W. |author4=Mikael Begtrup |author5=Daniel Bellus |author6=J. Berna-Canovas |author7=H. Boeckemeier |author8=Stefan Bräse |author9=I.R. Butler |author10=Jose Chiara |author11=Henri-J. Cristau |author12=I. Gorrell |author13=D. Keck |author14=Terence Kee |author15=Carmen Lopez-Leonardo |author16=T. Muller |author17=Patrick J. Murphy |author18=Patrick O'Leary |author19=Beate Priewisch |author20=L.K. Rasmussen |author21=Karola Rück-Braun |author22=Bjoern Schlummer |author23=Andreas Schmidt |author24=Paul James Stevenson |author25=J.C. Tebby |author26=David Virieux|title=Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 31b: Arene-X (X=N, P)|url=https://books.google.com/books?id=eiGGAwAAQBAJ&pg=PA1215|access-date=29 September 2014|date=2014-05-14|publisher=Georg Thieme Verlag|isbn=9783131720719|page=1215}}</ref>
⚫
Vanadyl nitrate can form a solid pale yellow adduct with [[boron trifluoride]].<ref name="Harris62"/> An adduct is also formed with [[acetonitrile]].<ref name="Dove1998"/>


⚫
Vanadyl nitrate form a solid pale yellow adduct with [[boron trifluoride]].<ref name="Harris62"/> An adduct is also formed with [[acetonitrile]].<ref name="Dove1998"/>
When mixed with petrol or l-hexene, or other unsaturated hydrocarbons, vanadyl nitrate ignites. It does not ignite with hexane.<ref name="Harris62"/> It reacts with paper rubber and wood, and ignites many organic solvents.<ref name=fed10>{{cite book|last1=Fedoroff|first1=Basil T|last2=Sheffield|first2=Oliver E |title=Encyclopedia of Explosives and Related Items Vol 10 of 10- U to Z|volume=10|page=V4|url=https://html1-f.scribdassets.com/5n1zz8vvr4sm3p8/images/136-c19277b6e3.jpg}}</ref>


⚫
<!--==Related compounds==
It can be used to nitrate various organic compounds at high yield when diluted with dichloromethane.<ref name="Dove1998">{{cite journal|last=Dove|first=Michael F. A.|author2=Berthold Manz |author3=John Montgomery |author4=Gerald Pattenden |author5=Simon A. Wood |year=1998|title=Vanadium(V) oxytrinitrate, VO(NO3)3. A powerful reagent for the nitration of aromatic compounds at room temperature under non-acidic conditions|journal=Journal of the Chemical Society, Perkin Transactions 1|issue=10|pages=1589–1590|issn=0300-922X|doi=10.1039/A801771I}}</ref> Nitrotoluene, [[methyl benzoate]] and [[benzoic acid]] are nitrated by prolonged exposure over a few days.<ref name="Dove1998"/> Benzonitrile does not react.<ref name="Dove1998"/> Benzene, toluene, tert-butylbenzene, halo-benzenes, ''ortho''-[[nitrotoluene]], [[anisole]], [[phenol]] and [[acetanilide]] are all rapidly nitrated within 30 minutes at room temperature.<ref name="Dove1998"/>

⚫
The ultraviolet spectrum of the liquid shows an absorption band peaking at 208&nbsp;nm with a shoulder at 242&nbsp;nm. At 55&nbsp;°C the gaseous vanadyl nitrate has absorption bands also at 486, 582 and 658&nbsp;nm in the visual light spectrum.<ref name=Varetti/> Liquid vanadyl nitrate has absorption lines in the infrared at 1880, 1633, 1612, 1560, 1306, 1205, 1016, 996, 965, 895, 783, 632, 457, 357, 301, 283, 234, 193, 133, 93 and 59&nbsp;cm<sup>−1</sup>.<ref name=Varetti/> 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&nbsp;cm<sup>−1</sup>.<ref name="Brandán2009"/> Many of these bands are due to stretching in nitrogen–oxygen bonds, but 1016.3&nbsp;cm<sup>−1</sup> 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.<ref name="Brandán2009"/>

⚫
==Related compounds==


===Hexammino-vanadium nitrate===
===Hexammino-vanadium nitrate===
Hexammino-vanadium nitrate V(NH<sub>3</sub>)<sub>6</sub>.(NO<sub>3</sub>)<sub>3</sub> was claimed to be formed by reacting hexamino vanadium trichloride with nitric acid.<ref name="Meyer1924">{{cite journal|last=Meyer|first=Julius|author2=Robert Backa|year=1924|title=Zur Kenntnis des dreiwertigen Vanadins. I|journal=Zeitschrift für anorganische und allgemeine Chemie|volume=135|issue=1|pages=177–193|issn=0863-1786|doi=10.1002/zaac.19241350113}}</ref> However doubt is cast on the existence of hexammino complexes of vanadium.<ref>{{cite book|last1=Cotton|first1=F. Albert|last2=Wilkinson|first2=Geoffrey|title=Advanced Inorganic Chemistry A Comprehensive Text|year=1966|publisher=John Wiley|page=817|edition=5}}</ref>
Hexammino-vanadium nitrate [V(NH<sub>3</sub>)<sub>6</sub>](NO<sub>3</sub>)<sub>3</sub> was claimed to be formed by reacting hexamino vanadium trichloride with nitric acid.<ref name="Meyer1924">{{cite journal|last=Meyer|first=Julius|author2=Robert Backa|year=1924|title=Zur Kenntnis des dreiwertigen Vanadins. I|journal=Zeitschrift für anorganische und allgemeine Chemie|volume=135|issue=1|pages=177–193|issn=0863-1786|doi=10.1002/zaac.19241350113}}</ref> However doubt is cast on the existence of hexammino complexes of vanadium.<ref>{{cite book|last1=Cotton|first1=F. Albert|last2=Wilkinson|first2=Geoffrey|title=Advanced Inorganic Chemistry A Comprehensive Text|year=1966|publisher=John Wiley|page=817|edition=5}}</ref>

⚫
===Vanadyl (IV) nitrate===
⚫
Vanadyl (IV) nitrate VO(NO<sub>3</sub>)<sub>2</sub> is made from vanadyl sulfate and barium nitrate, or vanadyl chloride and silver nitrate. It forms a blue solution, but cannot be crystallized, instead forming vanadium pentoxide when evaporated. Another method to make it as green blue needles is via vanadium pentoxide, oxalic acid and dilute nitric acid at 90&nbsp;°C, but the solid form is not confirmed.<ref name=fed10/><ref name="Honda">{{cite journal|last=Honda|first=Kenichi|date=May 1964|title=The Electrolytic Preparation of Vanadium(II) Developers|journal=Bulletin of the Chemical Society of Japan|volume=37|issue=5|pages=723–730|issn=1348-0634|url=https://www.jstage.jst.go.jp/article/bcsj1926/37/5/37_5_723/_pdf|doi=10.1246/bcsj.37.723|doi-access=free}}</ref>

===Mononitratodioxovanadium===
⚫
Vanadium metal reacts with [[dinitrogen tetroxide]] with an acetonitrile catalyst at 0&nbsp;°C to yield mononitratodioxovanadium(V), VO<sub>2</sub>NO<sub>3</sub>, a brick red solid.<ref>{{cite book|last1=Cotton|first1=F. Albert|last2=Wilkinson|first2=Geoffrey|title=Advanced Inorganic Chemistry A Comprehensive Text|year=1966|publisher=John Wiley|page=814|edition=5}}</ref><ref name="Pantonin1960">{{cite journal|last=Pantonin|first=John A.|author2=Albert K. Fischer |author3=Edward A. Heintz |year=1960|title=The preparation of mononitratodioxovanadium(V), VO2NO3|journal=Journal of Inorganic and Nuclear Chemistry|volume=14|issue=1–2|pages=145–147|issn=0022-1902|doi=10.1016/0022-1902(60)80220-5}}</ref> Mononitratodioxovanadium easily dissolves in water to make an orange solution, but this is unstable forming a deep brown gel after a day. VO<sub>2</sub>NO<sub>3</sub> cannot be crystallized from the solution, instead vanadium pentoxide results when a solution is evaporated. Also if VO<sub>2</sub>NO<sub>3</sub> is heated at 350&nbsp;°C, vanadium pentoxide solid is left behind.<ref name="Pantonin1960"/>


⚫
===Vanadyl(IV) nitrate===
Infrared absorption at 9.8 to 10 μm indicates vanadium to oxygen bonds are present, and absorption at 7.25&nbsp;μm indicates nitrate. Very weak absorption at 12.19&nbsp;μm shows a very small quantity of ionic nitrate exists, so this compound is mostly covalent.<ref name="Pantonin1960"/>
⚫
Vanadyl (IV) nitrate VO(NO<sub>3</sub>)<sub>2</sub> is prepared by treating [[vanadyl sulfate]] with [[barium nitrate]] as well as [[vanadyl chloride]] and [[silver nitrate]]. Its aqueous solutions are blue, evaporation of which gives [[vanadium pentoxide]]. Green-blue needles of the same compound are claimed to form via vanadium pentoxide, oxalic acid, and dilute nitric acid at 90&nbsp;°C.<ref name=fed10/><ref name="Honda">{{cite journal|last=Honda|first=Kenichi|date=May 1964|title=The Electrolytic Preparation of Vanadium(II) Developers|journal=Bulletin of the Chemical Society of Japan|volume=37|issue=5|pages=723–730|issn=1348-0634|url=https://www.jstage.jst.go.jp/article/bcsj1926/37/5/37_5_723/_pdf|doi=10.1246/bcsj.37.723|doi-access=free}}</ref>
-->


==References==
==References==
Line 87: Line 78:
*L. Bretherick, Ed, "Hazards in the Chemical Laboratory", Royal Society of Chemistry, London, Engl (1979), pg. 1160
*L. Bretherick, Ed, "Hazards in the Chemical Laboratory", Royal Society of Chemistry, London, Engl (1979), pg. 1160


{{Vanadium compounds}}
{{Nitrates}}
{{Nitrates}}


[[Category:Vanadium compounds]]
[[Category:Vanadium(V) compounds]]
[[Category:Nitrates]]
[[Category:Nitrates]]
[[Category:Vanadyl compounds]]

Latest revision as of 00:54, 13 December 2024

Vanadyl nitrate
Names
Other names
trinitratooxovanadium
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/3NO3.O.V/c3*2-1(3)4;;/q3*-1;;+3
    Key: NRKQBMOGOKEWPX-UHFFFAOYSA-N
  • [V](O[N+]([O-])=O)(O[N+]([O-])=O)(O[N+]([O-])=O)=O
Properties
VO(NO3)3
Molar mass 252.953 g/mol
Appearance yellow liquid.
Melting point 2 °C (36 °F; 275 K)[1]
Boiling point 86 to 91 °C (187 to 196 °F; 359 to 364 K) at 0.7mm Hg
Hydrolysis
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 oxidant
Related compounds
Related compounds
 titanium nitrate, vanadyl perchlorate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

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.[2]

Production

[edit]

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%.[3]

V2O5 + 3 N2O5 → 2 VO(NO3)3.

Purification can be achieved by vacuum distillation.[3]

Mononitratodioxovanadium (VO2NO3) is an intermediate in this synthesis. It is a brick red solid.[4][5]

Vanadyl nitrate can also be made from vanadyl trichloride VOCl3 and dinitrogen pentoxide.[6]

Structure

[edit]

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).[7][8]

Properties

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Vanadyl nitrate dissolves in dichloromethane, nitromethane, carbon tetrachloride, and saturated hydrocarbons.[1] 1-Hexene, or other unsaturated hydrocarbons ignite upon contact with vanadyl nitrate.[3][9] Upon contact with water, it irreversibly hydrolyzes, releasing nitric acid.[3][10]

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.[10] 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.[10] 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.[2] 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.[2]

Reactions

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It is a nitrating agent for aromatic compounds. Reactions proceed at room temperature. Often dichloromethane is used as an inert solvent.[1] Nitrotoluene, methyl benzoate and benzoic acid are nitrated by prolonged exposure over a few days.[1] Benzonitrile does not react.[1] [11]

Vanadyl nitrate form a solid pale yellow adduct with boron trifluoride.[3] An adduct is also formed with acetonitrile.[1]


References

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  1. ^ a b c d e f 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. doi:10.1039/A801771I. ISSN 0300-922X.
  2. ^ a b c 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. doi:10.1002/zaac.200801244. hdl:11336/53374. ISSN 0044-2313.
  3. ^ a b c d e Harris, Arlo D.; John C. Trebellas (26 April 1962). "AD296097 Experimental Studies of the Reactions of N2O5 with Metal Acid Anhydrides and BF3". Arlington Hall Station: Armed Services Technical Information Agency. Archived from the original on September 24, 2015. Retrieved 30 September 2014.
  4. ^ Cotton, F. Albert; Wilkinson, Geoffrey (1966). Advanced Inorganic Chemistry A Comprehensive Text (5 ed.). John Wiley. p. 814.
  5. ^ 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. doi:10.1016/0022-1902(60)80220-5. ISSN 0022-1902.
  6. ^ Schmeisser, Martin (1955). "Die Chemie der anorganischen Acylnitrate (ein Problem des Nitrylchlorids) und Acylperchlorate (ein Problem des Dichlorhexoxyds)". Angewandte Chemie (in German). 67 (17–18): 493–501. Bibcode:1955AngCh..67..493S. doi:10.1002/ange.19550671708. ISSN 0044-8249.
  7. ^ 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. doi:10.1039/A806710D. ISSN 0300-9246. (free download)
  8. ^ Davidson, G. (2000-01-01). Spectroscopic Properties of Inorganic and Organometallic Compounds. Royal Society of Chemistry. pp. 516–517. ISBN 9780854044269. Retrieved 30 September 2014.
  9. ^ Fedoroff, Basil T; Sheffield, Oliver E. Encyclopedia of Explosives and Related Items Vol 10 of 10- U to Z. Vol. 10. p. V4.[permanent dead link‍]
  10. ^ a b c Brandán, S.A.; A. Ben Altabef, E.L. Varetti; Varetti, E. L. (1995). "Vibrational and electronic spectra of vanadyl nitrate, VO(NO3)3". Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 51 (4): 669–675. Bibcode:1995AcSpA..51..669B. doi:10.1016/0584-8539(94)00154-4. ISSN 1386-1425.
  11. ^ 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 (2014-05-14). Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 31b: Arene-X (X=N, P). Georg Thieme Verlag. p. 1215. ISBN 9783131720719. Retrieved 29 September 2014.

Other reading

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  • Gmelin, Syst No 48, Teil A & Teil B (Lieferung 1 & 2) (1967); Teil A (Lieferung 1) & Teil A (Lieferung 2) (1968);& Erganzungwerk (Band2)(1971)
  • M. Schmeisser, "Chemical Abstracts", (1955), 49, 10873
  • L. Bretherick, Ed, "Hazards in the Chemical Laboratory", Royal Society of Chemistry, London, Engl (1979), pg. 1160
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