titanium(IV) nitrate

{{Chembox

| Watchedfields = changed

| verifiedrevid =

| ImageFile = Ti(NO3)4.tif

| ImageSize =

| ImageAlt =

| ImageCaption = Ball-and-stick model{{ cite journal | title = The crystal structures of anhydrous nitrates and their complexes. Part III. Titanium(IV) nitrate | first1 = C. D. | last1 = Garner | first2 = S. C. | last2 = Wallwork | journal = J. Chem. Soc. A | year = 1966 | pages = 1496–1500 | doi = 10.1039/J19660001496 }}{{ cite web | url = https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=1602029&DatabaseToSearch=Published | title = ICSD 26639 : ICSD Structure : N₄ O₁₂ Ti | author = | website = Cambridge Structural Database: Access Structures | publisher = Cambridge Crystallographic Data Centre | access-date = 2021-05-08 }}

| IUPACName =

| PIN =

| OtherNames = titanium tetranitrate, tetranitratotitanium

|Section1={{Chembox Identifiers

| CASNo_Ref = {{cascite|unchecked|??}}

| CASNo = 12372-56-4

| PubChem = 139314

| ChemSpiderID = 8123716

| ChemSpiderID_Ref = {{chemspidercite|changedt|chemspider}}

| InChI =1S/4NO3.Ti/c4*2-1(3)4;/q4*-1;+4

| InChIKey =QDZRBIRIPNZRSG-UHFFFAOYSA-N

| SMILES = [Ti](O[N+]([O-])=O)(O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O }}

|Section2={{Chembox Properties

| Formula = Ti(NO₃)₄

| MolarMass = 295.8866 g/mol

| Appearance = white volatile solid

| MeltingPtC = 58Chemistry of the Elements (Second Edition). N. N. Greenwood and A. Earnshaw. P₉₆₆. 21.3.4 Compounds with oxoanions

| BoilingPt = decompose

| Density = 2.192{{cite web|url=http://openmopac.net/PM7_accuracy/data_solids/Titanium_iv__nitrate__Ti_NO3_4__Jmol.html|title=Titanium(iv) nitrate (Ti(NO3)4)|accessdate=27 September 2014}}

| Solubility = Reacts{{cite book |author1=Nathaniel Howell Furman |author2=R. J. Mundy |author3=G. H. Morrison |title=The Distribution of Uranyl Nitrate from Aqueous Solutions to Diethyl Ether |date=1955 |publisher=U.S. Atomic Energy Commission. Technical Information Service |location=the University of Michigan |page=51 |language=English}} }}

|Section3={{Chembox Structure

| Structure_ref ={{cite journal|last=Garner|first=C. David|author2=Ian H. Hillier |author3=Martyn F. Guest |year=1975|title=Ab initio self-consistent field molecular-orbital calculation of the ground state of tetranitratotitanium(IV); comments on the reactivity of anhydrous metal nitrates|journal=Journal of the Chemical Society, Dalton Transactions|issue=19|page=1934|issn=0300-9246|doi=10.1039/DT9750001934}}

| CrystalStruct = monoclinic

| SpaceGroup = P2₁/C

| PointGroup =

| LattConst_a = 7.80

| LattConst_b = 13.57

| LattConst_c = 10.34 Å

| LattConst_alpha =

| LattConst_beta = 125·0

| LattConst_gamma =

| LattConst_ref =

| LattConst_Comment =

| UnitCellVolume = 896.52 Å³

| UnitCellFormulas = 4

| Coordination = 8

| MolShape = flattened tetrahedral

| OrbitalHybridisation =

| Dipole =

}}

|Section6={{Chembox Hazards

| MainHazards =

| FlashPt =

| AutoignitionPt =

}}

|Section8={{Chembox Related

| OtherCompounds = hafnium nitrate, zirconium nitrate, titanium phosphate, titanium perchlorate }}

}}

Titanium nitrate is the inorganic compound with formula Ti(NO₃)₄. It is a colorless, diamagnetic solid that sublimes readily. It is an unusual example of a volatile binary transition metal nitrate. Ill defined species called titanium nitrate are produced upon dissolution of titanium or its oxides in nitric acid.

Preparation

Similarly to its original method,{{cite journal|last=Reihlen|first=Hans|author2=Andreas Hake |year=1927|title=Über die Konstitution des N2O4 und N2O3 und die Additionsverbindungen von Nitro- und Nitrosokörpern an Zinn- und Titantetrachlorid|journal=Justus Liebig's Annalen der Chemie|volume=452|issue=1|pages=47–67|issn=0075-4617|doi=10.1002/jlac.19274520104|language=de}}{{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}} Ti(NO₃)₄ is prepared by the nitration of titanium tetrachloride using dinitrogen pentoxideP. Ehrlich "Titanium Tetranitrate" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1237. or chlorine nitrate:Schmeisser, M.; Brandle, K. Acyl nitrates and perchlorates. IV. ClNO3 as starting material for acyl nitrates. Angewandte Chemie, 1957. 69: 781. ISSN: 0044-8249.

:TiCl₄ + 4 N₂O₅ → Ti(NO₃)₄ + 4 ClNO₂

Hydrated titanium nitrate, the nitrate salt of the aquo complex [Ti(H₂O)₆]³⁺, is produced upon dissolution of titanium compounds in nitric acid.{{cite book|last1=Wiberg|first1=Egon|last2=Wiberg|first2=Nils|title=Inorganic Chemistry|url=https://books.google.com/books?id=Mtth5g59dEIC&pg=PA1331|accessdate=28 September 2014|year=2001|publisher=Academic Press|isbn=9780123526519|page=1331}}

Structure

The complex has D_2d symmetry, with four bidentate nitrate ligands. The N-O distances are 1·29 Å and 1·185 Å (noncoordinated).{{cite journal|last=Garner|first=C. David|author2=Ian H. Hillier |author3=Martyn F. Guest |year=1975|title=Ab initio self-consistent field molecular-orbital calculation of the ground state of tetranitratotitanium(IV); comments on the reactivity of anhydrous metal nitrates|journal=Journal of the Chemical Society, Dalton Transactions|issue=19|page=1934|issn=0300-9246|doi=10.1039/DT9750001934}}

Physical properties

In the infrared spectrum, it absorbs strongly at 1635 cm⁻¹, assigned to a N-O vibrational mode.{{cite journal|doi=10.1039/qr9712500289|title=Structural Aspects of Co-ordinated Nitrate Groups|year=1971|last1=Addison|first1=C. C.|last2=Logan|first2=N.|last3=Wallwork|first3=S. C.|last4=Garner|first4=C. D.|journal=Quarterly Reviews, Chemical Society|volume=25|issue=2|page=289}}

It is soluble in nonpolar solvents silicon tetrachloride and carbon tetrachloride.{{cite journal|last=Amos|first=D.W.|author2=G.W. Flewett |year=1974|title=Raman spectra of titanium (IV) and tin (IV) nitrates|journal=Spectrochimica Acta Part A: Molecular Spectroscopy|volume=30|issue=2|pages=453–461|issn=0584-8539|doi=10.1016/0584-8539(74)80085-1|bibcode=1974AcSpA..30..453A}}

Reactions

Titanium nitrate is hygroscopic, converting to ill-defined hydrates. The anhydrous material is highly reactive, even toward hydrocarbons.{{cite journal|last=Amos|first=D.W.|author2=D.A. Baines, G.W. Flewett|year=1973|title=Nitration by titanium (IV) nitrate|journal=Tetrahedron Letters|volume=14|issue=34|pages=3191–3194|issn=0040-4039|doi=10.1016/S0040-4039(00)79808-X}} Titanium nitrate also reacts with n-dodecane,{{cite journal|last=Coombes|first=Robert G.|author2=Leslie W. Russell |year=1974|title=Nitration of aromatic compounds by tetranitratotitanium(IV) in carbon tetrachloride solution|journal=Journal of the Chemical Society, Perkin Transactions 2|issue=7|page=830|issn=0300-9580|doi=10.1039/P29740000830}} p-dichlorobenzene, anisole, biphenyl,{{cite book|last=Schofield|first=Kenneth|title=Aromatic Nitration|url=https://books.google.com/books?id=N-08AAAAIAAJ&pg=PA97|accessdate=27 September 2014|year=1980|publisher=CUP Archive|isbn=9780521233620|pages=97–98}}

It decomposes thermally to titanium dioxide.{{cite book|last=Allendorf|first=Mark Donald|title=Proceedings of the Symposium on Fundamental Gas-Phase and Surface Chemistry of Vapor-Phase Materials Synthesis|chapter-url=https://books.google.com/books?id=TsTsmI1K40YC&pg=PA395|accessdate=27 September 2014|date=1999-01-01|publisher=The Electrochemical Society|isbn=9781566772174|pages=395–397|chapter=Titanium Oxide CVD from Titanium (IV) Nitrate ...}}

titanium(IV) nitrate

Preparation

Structure

Physical properties

Reactions

References

Other reading