Titanium nitrate

Titanium nitrate  File:Ti(NO3)4.tif

Ball-and-stick model[1][2]

Names
Other names

titanium tetranitrate, tetranitratotitanium

Identifiers

CAS Number

* 12372-56-4 N

3D model (JSmol)

* Interactive image

ChemSpider |

* 8123716 N

PubChem CID

* 139314

InChI

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

Key: QDZRBIRIPNZRSG-UHFFFAOYSA-N

SMILES

* [Ti](O[N+]([O-])=O)(O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O

Properties

Chemical formula

| Ti(NO3)4
Molar mass | 295.8866 g/mol
Appearance  | white volatile solid
Density | 2.192[3]
Melting point |  58.5 °C (137.3 °F; 331.6 K)
Boiling point | decompose

Solubility in water

| Reacts[4]
Structure[5]

Crystal structure

| monoclinic

Space group

| P21/C

Lattice constant

a = 7.80, b = 13.57, c = 10.34 Å

α = 90°, β = 125·0°, γ = 90°

Lattice volume (V)

| 896.52 Å3

Formula units (Z)

| 4

Coordination geometry

| 8

Molecular shape

| flattened tetrahedral
Related compounds

Related compounds

| hafnium nitrate, zirconium nitrate, titanium phosphate, titanium perchlorate

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Infobox references

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.

## Contents

* 1 Preparation
* 2 Structure
* 3 Physical properties
* 4 Reactions
* 5 References
* 6 Other reading

## Preparation

Similarly to its original method,[6][7] Ti(NO3)4 is prepared by the nitration of titanium tetrachloride using dinitrogen pentoxide:[8]

TiCl4 \+ 4 N2O5 → Ti(NO3)4 \+ 4 ClNO2

A hydrated titanium nitrate is produced upon dissolution of titanium compounds in nitric acid.[9]

## Structure

The complex has D2d symmetry, with four bidentate nitrate ligands. The N-O distances are 1·29 Å and 1·185 Å (noncoordinated).[5]

## Physical properties

In the infrared spectrum, it absorbs strongly at 1635 cm−1, assigned to a N-O vibrational mode.[10]

It is soluble in nonpolar solvents silicon tetrachloride and carbon tetrachloride.[11][7]

## Reactions

Titanium nitrate is hygroscopic, converting to ill-defined hydrates.[12] The anhydrous material is highly reactive, even toward hydrocarbons.[12] Titanium nitrate also reacts with n-dodecane,[13] p-dichlorobenzene, anisole, biphenyl,[13][14]

It decomposes thermally to titanium dioxide.[15]

## References

1. ↑ Garner, C. D.; Wallwork, S. C. (1966). "The crystal structures of anhydrous nitrates and their complexes. Part III. Titanium(IV) nitrate". J. Chem. Soc. A: 1496-1500. doi:10.1039/J19660001496.
2. ↑ "ICSD 26639 : ICSD Structure : N4 O12 Ti". Cambridge Crystallographic Data Centre. https://www.ccdc.cam.ac.uk/structures/Search?Ccdcid=1602029&DatabaseToSearch=Published.
3. ↑ "Titanium(iv) nitrate (Ti(NO3)4)". http://openmopac.net/PM7_accuracy/data_solids/Titanium_iv__nitrate__Ti_NO3_4__Jmol.html. Retrieved 27 September 2014.
4. ↑ Nathaniel Howell Furman; R. J. Mundy; G. H. Morrison (1955) (in English). The Distribution of Uranyl Nitrate from Aqueous Solutions to Diethyl Ether. the University of Michigan: U.S. Atomic Energy Commission. Technical Information Service. p. 51.
5. ↑ 5.0 5.1 Garner, C. David; Ian H. Hillier; Martyn F. Guest (1975). "Ab initio self-consistent field molecular-orbital calculation of the ground state of tetranitratotitanium(IV); comments on the reactivity of anhydrous metal nitrates". Journal of the Chemical Society, Dalton Transactions (19): 1934. doi:10.1039/DT9750001934. ISSN 0300-9246.
6. ↑ Reihlen, Hans; Andreas Hake (1927). "Über die Konstitution des N2O4 und N2O3 und die Additionsverbindungen von Nitro- und Nitrosokörpern an Zinn- und Titantetrachlorid" (in de). Justus Liebig's Annalen der Chemie 452 (1): 47–67. doi:10.1002/jlac.19274520104. ISSN 0075-4617.
7. ↑ 7.0 7.1 Schmeisser, Martin (1955). "Die Chemie der anorganischen Acylnitrate (ein Problem des Nitrylchlorids) und Acylperchlorate (ein Problem des Dichlorhexoxyds)" (in de). Angewandte Chemie 67 (17–18): 493–501. doi:10.1002/ange.19550671708. ISSN 0044-8249.
8. ↑ P. Ehrlich "Titanium Tetranitrate" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1237.
9. ↑ Wiberg, Egon; Wiberg, Nils (2001). Inorganic Chemistry. Academic Press. p. 1331. ISBN 9780123526519. https://books.google.com/books?id=Mtth5g59dEIC&pg=PA1331. Retrieved 28 September 2014.
10. ↑ C. C. Addison, N. Logan, S. C. Wallwork and C. D. Garner, "Structural Aspects of Coordinated Nitrate Groups" Quart. Rev., Chem. Soc., 1971, volume 25, 289-322. doi:10.1039/qr9712500289.
11. ↑ Amos, D.W.; G.W. Flewett (1974). "Raman spectra of titanium (IV) and tin (IV) nitrates". Spectrochimica Acta Part A: Molecular Spectroscopy 30 (2): 453–461. doi:10.1016/0584-8539(74)80085-1. ISSN 0584-8539. Bibcode: 1974AcSpA..30..453A.
12. ↑ 12.0 12.1 Amos, D.W.; D.A. Baines, G.W. Flewett (1973). "Nitration by titanium (IV) nitrate". Tetrahedron Letters 14 (34): 3191–3194. doi:10.1016/S0040-4039(00)79808-X. ISSN 0040-4039.
13. ↑ 13.0 13.1 Coombes, Robert G.; Leslie W. Russell (1974). "Nitration of aromatic compounds by tetranitratotitanium(IV) in carbon tetrachloride solution". Journal of the Chemical Society, Perkin Transactions 2 (7): 830. doi:10.1039/P29740000830. ISSN 0300-9580.
14. ↑ Schofield, Kenneth (1980). Aromatic Nitration. CUP Archive. pp. 97–98. ISBN 9780521233620. https://books.google.com/books?id=N-08AAAAIAAJ&pg=PA97. Retrieved 27 September 2014.
15. ↑ Allendorf, Mark Donald (1999-01-01). "Titanium Oxide CVD from Titanium (IV) Nitrate ...". Proceedings of the Symposium on Fundamental Gas-Phase and Surface Chemistry of Vapor-Phase Materials Synthesis. The Electrochemical Society. pp. 395–397. ISBN 9781566772174. https://books.google.com/books?id=TsTsmI1K40YC&pg=PA395. Retrieved 27 September 2014.

## Other reading

* Partington, J. R.; A. L. Whynes (1949). "660. Reactions of nitrosyl chloride. Part II". Journal of the Chemical Society (Resumed): 3135. doi:10.1039/JR9490003135. ISSN 0368-1769.
* Dauerman, L.; G.E. Salser (1973). "Mass spectra of covalent inorganic nitrates: copper(II) nitrate and titanium(IV) nitrate". Journal of Inorganic and Nuclear Chemistry 35 (1): 304–306. doi:10.1016/0022-1902(73)80643-8. ISSN 0022-1902.

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* t
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Titanium compounds

Titanium(II)|

* TiCl2
* TiH2
* TiO
* TiS
* TiSi2

| Organotitanium(II) compounds|

[(C5H5)2Ti(CO)2]

|

Titanium(III)|

* TiAl
* TiBr3
* TiCl3
* TiF3
* TiI3
* TiN
* TiP
* Ti2O3
* Ti2S3

| Organotitanium(III) compounds|

[(C5H5)2TiCl]2

|

Titanium(IV)|

* TiB2
* TiBr4
* TiC
* TiCl4
* Ti(ClO4)4
* TiF4
* H2TiF6
* TiH4
* TiI4
* Ti(NMe2)4
* Ti(NO3)4
* TiO2
* H4TiO4
* Ti4(OCH2CH3)16
* Ti(OCH(CH3)2)4
* Ti(OCH2CH2CH2CH3)4
* KTiOPO4
* NiO*Sb2O3*20TiO2
* TiS2
* TiSe2
* TiSi2

| Titanate compounds|

* BaTiO3
* Ba2TiO4
* Bi4Ti3O12
* CaTiO3
* CaCu3Ti4O12
* CaZrTi2O7
* Cs2TiO3
* Dy2Ti2O7
* EuBaTiO4
* FeTiO3
* Ho2Ti2O7
* Li2TiO3
* MnTiO3
* Na2Ti3O7
* Na0.5Bi0.5TiO3
* NiTiO3
* PbTiO3
* Pb(Zr,Ti)O3
* SrTiO3
* ZnTiO3

|

Organotitanium(IV) compounds|

* [(C5H5)2TiCl2]
* [(C5H5)2Ti(CH3)2]
* [(C5H5)2TiS5]
* [(C5H5)2Ti(μ-Cl)(μ-CH2)Al(CH3)2]
* [(η5-C5H4-CH2C6H4OCH3)2TiCl2]

|

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* e

Salts and covalent derivatives of the nitrate ion

HNO3 |  |  |  | He

|
|
|
|

LiNO3 | Be(NO3)2 | B(NO3)−4 | C  | NO−3,
NH4NO3 | O  | FNO3 | Ne
NaNO3 | Mg(NO3)2 | Al(NO3)3 | Si  | P  | S  | ClONO2 | Ar
KNO3 | Ca(NO3)2 | Sc(NO3)3 | Ti(NO3)4 | VO(NO3)3 | Cr(NO3)3 | Mn(NO3)2 | Fe(NO3)3,
Fe(NO3)2 | Co(NO3)2,
Co(NO3)3 | Ni(NO3)2 | Cu(NO3)2 | Zn(NO3)2 | Ga(NO3)3 | Ge  | As  | Se  | Br  | Kr
RbNO3 | Sr(NO3)2 | Y(NO3)3 | Zr(NO3)4 | Nb  | Mo  | Tc  | Ru  | Rh  | Pd(NO3)2 | AgNO3 | Cd(NO3)2 | In  | Sn  | Sb(NO3)3 | Te  | I  | Xe(NO3)2
CsNO3 | Ba(NO3)2 |  | Hf  | Ta  | W  | Re  | Os  | Ir  | Pt  | Au  | Hg2(NO3)2,
Hg(NO3)2 | Tl(NO3)3,
TlNO3 | Pb(NO3)2 | Bi(NO3)3
BiO(NO3) | Po  | At  | Rn
FrNO3 | Ra(NO3)2 |  | Rf  | Db  | Sg  | Bh  | Hs  | Mt  | Ds  | Rg  | Cn  | Nh  | Fl  | Mc  | Lv  | Ts  | Og
| ↓  |  |
La(NO3)3 | Ce(NO3)3,
Ce(NO3)4 | Pr  | Nd(NO3)3 | Pm  | Sm  | Eu(NO3)3 | Gd(NO3)3 | Tb(NO3)3 | Dy  | Ho  | Er  | Tm  | Yb  | Lu
Ac(NO3)3 | Th(NO3)4 | Pa  | UO2(NO3)2 | Np  | Pu  | Am  | Cm  | Bk  | Cf  | Es  | Fm  | Md  | No  | Lr

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