Hafnium tetrachloride

Hafnium(IV) chloride is the inorganic compound with the formula HfCl₄. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

Hafnium(IV) chloride

Names
IUPAC names Hafnium(IV) chloride Hafnium tetrachloride
Identifiers
CAS Number	13499-05-3^Y
3D model (JSmol)	Interactive image
ChemSpider	34591^Y
ECHA InfoCard	100.033.463
PubChem CID	37715
UNII	CNZ9V5JM5H^Y
CompTox Dashboard (EPA)	DTXSID0065513
InChI InChI=1S/4ClH.Hf/h4*1H;/q;;;;+4/p-4^Y Key: PDPJQWYGJJBYLF-UHFFFAOYSA-J^Y InChI=1/4ClH.Hf/h4*1H;/q;;;;+4/p-4 Key: PDPJQWYGJJBYLF-XBHQNQODAR
SMILES Cl[Hf](Cl)(Cl)Cl
Properties
Chemical formula	HfCl4
Molar mass	320.302 g/mol
Appearance	white crystalline solid
Density	3.89 g/cm^3[1]
Melting point	432 °C (810 °F; 705 K)
Solubility in water	decomposes[2]
Vapor pressure	1 mmHg at 190 °C
Structure
Crystal structure	Monoclinic, mP10[1]
Space group	C2/c, No. 13
Lattice constant	a = 0.6327 nm, b = 0.7377 nm, c = 0.62 nm
Coordination geometry	4
Hazards
Main hazards	irritant and corrosive
Safety data sheet	MSDS
Flash point	Non-flammable
Lethal dose or concentration (LD, LC):
LD50 (median dose)	2362 mg/kg (rat, oral)[3]
Related compounds
Other anions	Hafnium tetrafluoride Hafnium(IV) bromide Hafnium(IV) iodide
Other cations	Titanium(IV) chloride Zirconium(IV) chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Preparation

HfCl₄ can be produced by several related procedures:

• The reaction of carbon tetrachloride and hafnium oxide at above 450 °C;[4][5]

HfO₂ + 2 CCl₄ → HfCl₄ + 2 COCl₂

• Chlorination of a mixture of HfO₂ and carbon above 600 °C using chlorine gas or sulfur monochloride:[6][7]

HfO₂ + 2 Cl₂ + C → HfCl₄ + CO₂

• Chlorination of hafnium carbide above 250 °C.[8]

Separation of Zr and Hf

Hafnium and zirconium occur together in minerals such as zircon, cyrtolite and baddeleyite. Zircon contains 0.05% to 2.0% hafnium dioxide HfO₂, cyrtolite with 5.5% to 17% HfO₂ and baddeleyite contains 1.0 to 1.8 percent HfO₂.[9] Hafnium and zirconium compounds are extracted from ores together and converted to a mixture of the tetrachlorides.

The separation of HfCl₄ and ZrCl₄ is difficult because the compounds of Hf and Zr have very similar chemical and physical properties. Their atomic radii are similar: the atomic radius is 156.4 pm for hafnium, whereas that of Zr is 160 pm.[10] These two metals undergo similar reactions and form similar coordination complexes.

A number of processes have been proposed to purify HfCl₄ from ZrCl₄ including fractional distillation, fractional precipitation, fractional crystallization and ion exchange. The log (base 10) of the vapor pressure of solid hafnium chloride (from 476 to 681 K) is given by the equation: log₁₀ P = −5197/T + 11.712, where the pressure is measured in torrs and temperature in kelvins. (The pressure at the melting point is 23,000 torrs.)[11]

One method is based on the difference in the reducibility between the two tetrahalides.[9] The tetrahalides can in be separated by selectively reducing the zirconium compound to one or more lower halides or even zirconium. The hafnium tetrachloride remains substantially unchanged during the reduction and may be recovered readily from the zirconium subhalides. Hafnium tetrachloride is volatile and can therefore easily be separated from the involatile zirconium trihalide.

Structure and bonding

This group 4 halide contains hafnium in the +4 oxidation state. Solid HfCl₄ is a polymer with octahedral Hf centers. Of the six chloride ligands surrounding each Hf centre, two chloride ligands are terminal and four bridge to another Hf centre. In the gas phase, both ZrCl₄ and HfCl₄ adopt the monomeric tetrahedral structure seen for TiCl₄.[12] Electronographic investigations of HfCl₄ in gas phase showed that the Hf-Cl internuclear distance is 2.33 Å and the Cl…Cl internuclear distance is 3.80 Å. The ratio of intenuclear distances r(Me-Cl)/r(Cl…Cl) is 1.630 and this value agrees well with the value for the regular tetrahedron model (1.633).[10]

Reactivity

Structure of HfCl₄(thf)₂.[13]

The compound hydrolyzes, evolving hydrogen chloride:

HfCl₄ + H₂O → HfOCl₂ + 2 HCl

Aged samples thus often are contaminated with oxychlorides, which are also colourless.

THF forms a monomeric 2:1 complex:[14]

HfCl₄ + 2 OC₄H₈ → HfCl₄(OC₄H₈)₂

Because this complex is soluble in organic solvents, it is a useful reagent for preparing other complexes of hafnium.

HfCl₄ undergoes salt metathesis with Grignard reagents. In this way, tetrabenzylhafnium can be prepared.

With alcohols, alkoxides are formed.

HfCl₄ + 4 ROH → Hf(OR)₄ + 4 HCl

These compounds adopt complicated structures.

Reduction

Reduction of HfCl₄ is especially difficult. In the presence of phosphine ligands, reduction can be effected with potassium-sodium alloy:[15]

2 HfCl₄ + 2 K + 4 P(C₂H₅)₃ → Hf₂Cl₆[P(C₂H₅)₃]₄ + 2 KCl

The deep green dihafnium product is diamagnetic. X-ray crystallography shows that the complex adopts an edge-shared bioctahedral structure, very similar to the Zr analogue.

Uses

Hafnium tetrachloride is the precursor to highly active catalysts for the Ziegler-Natta polymerization of alkenes, especially propylene.[16] Typical catalysts are derived from tetrabenzylhafnium.

HfCl₄ is an effective Lewis acid for various applications in organic synthesis. For example, ferrocene is alkylated with allyldimethylchlorosilane more efficiently using hafnium chloride relative to aluminium trichloride. The greater size of Hf may diminish HfCl₄'s tendency to complex to ferrocene.[17]

HfCl₄ increases the rate and control of 1,3-dipolar cycloadditions.[18] It was found to yield better results than other Lewis acids when used with aryl and aliphatic aldoximes, allowing specific exo-isomer formation.

Microelectronics applications

HfCl₄ was considered as a precursor for chemical vapor deposition and atomic layer deposition of hafnium dioxide and hafnium silicate, used as high-k dielectrics in manufacture of modern high-density integrated circuits.[19] However, due to its relatively low volatility and corrosive byproducts (namely, HCl), HfCl₄ was phased out by metal-organic precursors, such as tetrakis ethylmethylamino hafnium (TEMAH).[20]

References

1. Niewa R., Jacobs H. (1995) Z. Kristallogr. 210: 687
2. Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, FL: CRC Press. p. 4.66. ISBN 1439855110.
3. "Hafnium compounds (as Hf)". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
4. Kirk-Othmer Encyclopedia of Chemical Technology. 11 (4th ed.). 1991.
5. Hummers, W. S.; Tyree, Jr., S. Y.; Yolles, S. (1953). Zirconium and Hafnium Tetrachlorides. Inorganic Syntheses. 4. p. 121. doi:10.1002/9780470132357.ch41. ISBN 9780470132357.
6. Hopkins, B. S. (1939). "13 Hafnium". Chapters in the chemistry of less familiar elements. Stipes Publishing. p. 7.
7. Hála, Jiri (1989). Halides, oxyhalides and salts of halogen complexes of titanium, zirconium, hafnium, vanadium, niobium and tantalum. 40 (1st ed.). Oxford: Pergamon. pp. 176–177. ISBN 978-0080362397.
8. Elinson, S. V. and Petrov, K. I. (1969) Analytical Chemistry of the Elements: Zirconium and Hafnium. 11.
9. Newnham, Ivan Edgar "Purification of Hafnium Tetrachloride". U.S. Patent 2,961,293 November 22, 1960.
10. Spiridonov, V. P.; Akishin, P. A.; Tsirel'Nikov, V. I. (1962). "Electronographic investigation of the structure of zirconium and hafnium tetrachloride molecules in the gas phase". Journal of Structural Chemistry. 3 (3): 311. doi:10.1007/BF01151485.
11. Palko, A. A.; Ryon, A. D.; Kuhn, D. W. (1958). "The Vapor Pressures of Zirconium Tetrachloride and Hafnium Tetrachloride". The Journal of Physical Chemistry. 62 (3): 319. doi:10.1021/j150561a017. hdl:2027/mdp.39015086446302.
12. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 964–966. ISBN 978-0-08-037941-8.
13. Duraj, S. A.; Towns; Baker; Schupp, J. (1990). "Structure of cis-Tetrachlorobis(tetrahydrofuran)hafnium(IV)". Acta Crystallographica. C46 (5): 890–2. doi:10.1107/S010827018901382X.
14. Manzer, L. E. (1982). "Tetrahydrofuran Complexes of Selected Early Transition Metals". Inorg. Synth. 21: 135–140. doi:10.1002/9780470132524.ch31. ISBN 978-0-470-13252-4.
15. Riehl, M. E.; Wilson, S. R.; Girolami, G. S. (1993). "Synthesis, X-ray Crystal Structure, and Phosphine-Exchange Reactions of the Hafnium(III)-Hafnium(III) Dimer Hf₂Cl₆[P(C₂H₅)₃]₄". Inorg. Chem. 32 (2): 218–222. doi:10.1021/ic00054a017.
16. Ron Dagani (2003-04-07). "Combinatorial Materials: Finding Catalysts Faster". Chemical and Engineering News. p. 10.
17. Ahn, S.; Song, Y. S.; Yoo, B. R.; Jung, I. N. (2000). "Lewis Acid-Catalyzed Friedel−Crafts Alkylation of Ferrocene with Allylchlorosilanes". Organometallics. 19 (14): 2777. doi:10.1021/om0000865.
18. Graham, A. B.; Grigg, R.; Dunn, P. J.; Higginson, P. (2000). "Tandem 1,3-azaprotiocyclotransfer–cycloaddition reactions between aldoximes and divinyl ketone. Remarkable rate enhancement and control of cycloaddition regiochemistry by hafnium(iv) chloride". Chemical Communications (20): 2035–2036. doi:10.1039/b005389i.
19. Choi, J. H.; Mao, Y.; Chang, J. P. (2011). "Development of hafnium based high-k materials—A review". Materials Science and Engineering: R: Reports. 72 (6): 97. doi:10.1016/j.mser.2010.12.001.
20. Robertson, J. (2006). "High dielectric constant gate oxides for metal oxide Si transistors". Reports on Progress in Physics. 69 (2): 327–396. Bibcode:2006RPPh...69..327R. doi:10.1088/0034-4885/69/2/R02.