Titanium nitrate

Titanium nitrate

Names
Other names titanium tetranitrate, tetranitratotitanium
Identifiers
CAS Number	12372-56-4
3D model (Jmol)	Interactive image
ChemSpider	8123716
ECHA InfoCard	100.222.601
PubChem	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
Melting point	58.5 °C (137.3 °F; 331.6 K)
Boiling point	decompose
Solubility in water	carbon tetrachloride (0.1 mol/L at 10 °C).[1]
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.

Preparation

Similarly to its original method,^[2][3] Ti(NO₃)₄ is prepared by the nitration of titanium tetrachloride using dinitrogen pentoxide:^[4]

TiCl₄ + 4 N₂O₅ → Ti(NO₃)₄ + 4 ClNO₂

A hydrated titanium nitrate 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] or .^[3]

Reactions

Titanium nitrate is hygroscopic, converting to ill-defined hydrates.^[9] The anhydrous material is highly reactive, even toward hydrocarbons.^[9] Titanium nitrate also reacts with n-dodecane,^[1] p-dichlorobenzene, anisole, biphenyl,^[1][10]

It decomposes thermally to titanium dioxide.^[11]

References

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.
2. 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 (in German). 452 (1): 47–67. doi:10.1002/jlac.19274520104. ISSN 0075-4617.
3. 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. doi:10.1002/ange.19550671708. ISSN 0044-8249.
4. P. Ehrlich "Titanium Tetranitrate" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1237.
5. Wiberg, Egon; Wiberg, Nils (2001). Inorganic Chemistry. Academic Press. p. 1331. ISBN 9780123526519. Retrieved 28 September 2014.
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. doi:10.1039/DT9750001934. ISSN 0300-9246.
7. 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.
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. Bibcode:1974AcSpA..30..453A. doi:10.1016/0584-8539(74)80085-1. ISSN 0584-8539.
9. 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.
10. Schofield, Kenneth (1980). Aromatic Nitration. CUP Archive. pp. 97–98. ISBN 9780521233620. Retrieved 27 September 2014.
11. 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. 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.

Salts and covalent derivatives of the Nitrate ion
HNO3																	He
LiNO3	Be(NO3)2											B(NO3)4^−	C	N	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	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	Zr(NO3)4	Nb	Mo	Tc	Ru	Rh	Pd(NO3)2	AgNO3	Cd(NO3)2	In	Sn	Sb	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	Pb(NO3)2	Bi(NO3)3 BiO(NO3)	Po	At	Rn
Fr	Ra		Rf	Db	Sg	Bh	Hs	Mt	Ds	Rg	Cn	Nh	Fl	Mc	Lv	Ts	Og
		↓
		La	Ce(NO3)3, Ce(NO3)4	Pr	Nd	Pm	Sm	Eu	Gd(NO3)3	Tb	Dy	Ho	Er	Tm	Yb	Lu
		Ac	Th	Pa	UO2(NO3)2	Np	Pu	Am	Cm	Bk	Cf	Es	Fm	Md	No	Lr