Titanium(IV) nitrate explained

Titanium(IV) nitrate should not be confused with Titanium nitride.

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,^{[1] [2]} Ti(NO₃)₄ is prepared by the nitration of titanium tetrachloride using dinitrogen pentoxide^[3] or chlorine nitrate:^[4]

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.^[5]

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).^[6]

Physical properties

In the infrared spectrum, it absorbs strongly at 1635 cm⁻¹, assigned to a N-O vibrational mode.^[7]

It is soluble in nonpolar solvents silicon tetrachloride and carbon tetrachloride.^{[8] [2]}

Reactions

Titanium nitrate is hygroscopic, converting to ill-defined hydrates. The anhydrous material is highly reactive, even toward hydrocarbons.^[9] Titanium nitrate also reacts with n-dodecane,^[10] p-dichlorobenzene, anisole, biphenyl,^{[10] [11]}

It decomposes thermally to titanium dioxide.^[12]

Other reading

• Partington. J. R.. A. L. Whynes . 1949. 660. Reactions of nitrosyl chloride. Part II. Journal of the Chemical Society (Resumed). 3135. 0368-1769. 10.1039/JR9490003135.
• 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. 0022-1902. 10.1016/0022-1902(73)80643-8.

Notes and References

1. Reihlen. Hans. Andreas Hake . 1927. Über die Konstitution des N2O4 und N2O3 und die Additionsverbindungen von Nitro- und Nitrosokörpern an Zinn- und Titantetrachlorid. Justus Liebig's Annalen der Chemie. 452. 1. 47–67. 0075-4617. 10.1002/jlac.19274520104. de.
2. 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.
3. P. Ehrlich "Titanium Tetranitrate" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1237.
4. Schmeisser, M.; Brandle, K. Acyl nitrates and perchlorates. IV. ClNO3 as starting material for acyl nitrates. Angewandte Chemie, 1957. 69: 781. ISSN: 0044-8249.
5. Book: Wiberg. Egon. Wiberg. Nils. Inorganic Chemistry. 28 September 2014. 2001. Academic Press. 9780123526519. 1331.
6. 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. 0300-9246. 10.1039/DT9750001934.
7. 10.1039/qr9712500289. Structural Aspects of Co-ordinated Nitrate Groups. 1971. Addison. C. C.. Logan. N.. Wallwork. S. C.. Garner. C. D.. Quarterly Reviews, Chemical Society. 25. 2. 289.
8. 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. 0584-8539. 10.1016/0584-8539(74)80085-1. 1974AcSpA..30..453A.
9. Amos. D.W.. D.A. Baines, G.W. Flewett. 1973. Nitration by titanium (IV) nitrate. Tetrahedron Letters. 14. 34. 3191–3194. 0040-4039. 10.1016/S0040-4039(00)79808-X.
10. 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. 0300-9580. 10.1039/P29740000830.
11. Book: Schofield, Kenneth. Aromatic Nitration. 27 September 2014. 1980. CUP Archive. 9780521233620. 97–98.
12. Book: Allendorf, Mark Donald. Proceedings of the Symposium on Fundamental Gas-Phase and Surface Chemistry of Vapor-Phase Materials Synthesis. https://books.google.com/books?id=TsTsmI1K40YC&pg=PA395. 27 September 2014. 1999-01-01. The Electrochemical Society. 9781566772174. 395–397. Titanium Oxide CVD from Titanium (IV) Nitrate ....