Europium(III) chloride

Europium(III) chloride
Names
	IUPAC names Europium(III) chloride; Europium trichloride
Identifiers
CAS Number	10025-76-0 ; 13759-92-7 (hexahydrate) ;
3D model (JSmol)	Interactive image;
ChemSpider	23194 ;
ECHA InfoCard	100.030.025
EC Number	233-040-4;
PubChem CID	24809;
RTECS number	LE7525000;
UNII	LP6WL6W368 ;
CompTox Dashboard (EPA)	DTXSID2041965 ;
	InChI InChI=1S/3ClH.Eu/h31H;/q;;;+3/p-3 Key: NNMXSTWQJRPBJZ-UHFFFAOYSA-K ; InChI=1/3ClH.Eu/h31H;/q;;;+3/p-3 Key: NNMXSTWQJRPBJZ-DFZHHIFOAZ;
	SMILES Cl[Eu](Cl)Cl;
Properties
Chemical formula	EuCl3
Molar mass	258.323 g/mol; 366.41 g/mol (hexahydrate)
Melting point	632 °C (1,170 °F; 905 K) decomposes
Solubility in other solvents	Soluble
Structure
Crystal structure	hexagonal (UCl3 type), hP8
Space group	P63/m, No. 176
Coordination geometry	Tricapped trigonal prismatic; (nine-coordinate)
Related compounds
Other anions	Europium(III) oxide
Other cations	Samarium(III) chloride; Gadolinium(III) chloride
Related compounds	Europium dichloride
	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

Europium(III) chloride is an inorganic compound with the formula EuCl₃. The anhydrous compound is a yellow solid. Being hygroscopic it rapidly absorbs water to form a white crystalline hexahydrate, EuCl₃·6H₂O, which is colourless. The compound is used in research.

Preparation

Treating Eu₂O₃ with aqueous HCl produces hydrated europium chloride (EuCl₃·6H₂O). This salt cannot be rendered anhydrous by heating. Instead one obtains an oxychloride. Anhydrous EuCl₃ is often prepared by the "ammonium chloride route," starting from either Eu₂O₃[1][2] or hydrated europium chloride (EuCl₃·6H₂O) by heating carefully to 230 °C.[3] These methods produce (NH₄)₂[EuCl₅]:

10 NH₄Cl + Eu₂O₃ → 2 (NH₄)₂[EuCl₅] + 6 NH₃ + 3 H₂O

EuCl₃·6H₂O + 2 NH₄Cl → (NH₄)₂[EuCl₅] + 6 H₂O

The pentachloride decomposes thermally according to the following equation:

(NH₄)₂[EuCl₅] → 2 NH₄Cl + EuCl₃

The thermolysis reaction proceeds via the intermediary of (NH₄)[Eu₂Cl₇].

Reactions

Europium(III) chloride is a precursor to other europium compounds. It can be converted to the corresponding metal bis(trimethylsilyl)amide via salt metathesis with lithium bis(trimethylsilyl)amide.[4] The reaction is performed in THF and requires a period at reflux.

EuCl₃ + 3 LiN(SiMe₃)₂ → Eu(N(SiMe₃)₂)₃ + 3 LiCl

Eu(N(SiMe₃)₂)₃ is a starting material for the more complicated coordination complexes.

Reduction with hydrogen gas with heating gives EuCl₂. The latter has been used to prepare organometallic compounds of europium(II), such as bis(pentamethylcyclopentadienyl)europium(II) complexes.[5][6] Europium(III) chloride can be used as a starting point for the preparation of other europium salts.

Structure

In the solid state, it crystallises in the UCl₃ motif. The Eu centres are nine-coordinate.[7]

Space-filling image of EuCl₃.

Bibliography

Weast, R. C., ed. (1972). Handbook of Chemistry and Physics (53rd ed.). Cleveland, OH: Chemical Rubber Co.

References

Meyer, G. (1989). The Ammonium Chloride Route to Anhydrous Rare Earth Chlorides-The Example of YCl₃. Inorganic Syntheses. 25. pp. 146–150. doi:10.1002/9780470132562.ch35. ISBN 978-0-470-13256-2.
Edelmann, F. T.; Poremba, P. (1997). Herrmann, W. A. (ed.). Synthetic Methods of Organometallic and Inorganic Chemistry. VI. Stuttgart: Georg Thieme Verlag. ISBN 3-13-103021-6.
Taylor, M.D.; Carter, C.P. (1962). "Preparation of anhydrous lanthanide halides, especially iodides". Journal of Inorganic and Nuclear Chemistry. 24 (4): 387–391. doi:10.1016/0022-1902(62)80034-7.
Bradley, Donald C.; Ghotra, Joginder S.; Hart, F. Alan (1973). "Low co-ordination numbers in lanthanide and actinide compounds. Part I. The preparation and characterization of tris{bis(trimethylsilyl)-amido}lanthanides". Journal of the Chemical Society, Dalton Transactions (10): 1021. doi:10.1039/DT9730001021.
Tilley, T. Don; Andersen, Richard A.; Spencer, Brock; Ruben, Helena; Zalkin, Allan; Templeton, David H. (1980). "Divalent lanthanide chemistry. Bis (pentamethylcyclopentadienyl) europium(II) and -ytterbium(II) derivatives: crystal structure of bis (pentamethylcyclopentadienyl) (tetrahydrofuran ytterbium(II) -hemitoluene at 176 K". Inorganic Chemistry. 19 (10): 2999. doi:10.1021/ic50212a031.
Evans, William J.; Hughes, Laura A.; Hanusa, Timothy P. (1986). "Synthesis and x-ray crystal structure of bis(pentamethylcyclopentadienyl) complexes of samarium and europium: (C₅Me₅)₂Sm and (C₅Me₅)₂Eu". Organometallics. 5 (7): 1285. doi:10.1021/om00138a001.
Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.

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[1] Meyer, G. (1989). The Ammonium Chloride Route to Anhydrous Rare Earth Chlorides-The Example of YCl₃. Inorganic Syntheses. 25. pp. 146–150. doi:10.1002/9780470132562.ch35. ISBN 978-0-470-13256-2.

[EdelmannPoremba1997-2] Edelmann, F. T.; Poremba, P. (1997). Herrmann, W. A. (ed.). Synthetic Methods of Organometallic and Inorganic Chemistry. VI. Stuttgart: Georg Thieme Verlag. ISBN 3-13-103021-6.

[3] Taylor, M.D.; Carter, C.P. (1962). "Preparation of anhydrous lanthanide halides, especially iodides". Journal of Inorganic and Nuclear Chemistry. 24 (4): 387–391. doi:10.1016/0022-1902(62)80034-7.

[lan-4] Bradley, Donald C.; Ghotra, Joginder S.; Hart, F. Alan (1973). "Low co-ordination numbers in lanthanide and actinide compounds. Part I. The preparation and characterization of tris{bis(trimethylsilyl)-amido}lanthanides". Journal of the Chemical Society, Dalton Transactions (10): 1021. doi:10.1039/DT9730001021.

[5] Tilley, T. Don; Andersen, Richard A.; Spencer, Brock; Ruben, Helena; Zalkin, Allan; Templeton, David H. (1980). "Divalent lanthanide chemistry. Bis (pentamethylcyclopentadienyl) europium(II) and -ytterbium(II) derivatives: crystal structure of bis (pentamethylcyclopentadienyl) (tetrahydrofuran ytterbium(II) -hemitoluene at 176 K". Inorganic Chemistry. 19 (10): 2999. doi:10.1021/ic50212a031.

[6] Evans, William J.; Hughes, Laura A.; Hanusa, Timothy P. (1986). "Synthesis and x-ray crystal structure of bis(pentamethylcyclopentadienyl) complexes of samarium and europium: (C₅Me₅)₂Sm and (C₅Me₅)₂Eu". Organometallics. 5 (7): 1285. doi:10.1021/om00138a001.

[7] Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.