Chemistry:Lanthanide chlorides
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Short description: Chemical compounds between a lanthanide element and chlorine
Lanthanide chlorides are a group of chemical compounds that can form between a lanthanide element (from lanthanum to lutetium) and chlorine. The lanthanides in these compounds are usually in the +2 and +3 oxidation states, although compounds with lanthanides in lower oxidation states exist.
Lanthanide dichlorides
Divalent chlorides are formed by neodymium, samarium, europium, dysprosium, thulium and ytterbium. They can be prepared by reducing the trivalent chloride with lithium metal/naphthalene in tetrahydrofuran:[1]
- LnCl3 + Li → LnCl2 + LiCl (Ln=Nd,Sm,Eu)
Reducing the chloride with the metal or hydrogen is also possible:[2][3]
- 2 LnCl3 + Ln → 3 LnCl2 (Ln=Nd,Sm,Eu?,Dy,Tm,Yb)
- 2 LnCl3 + H2 → 2 LnCl2 + 2 HCl (Ln=Nd,Sm,Eu,Dy,Tm,Yb)
Lanthanide trichlorides
The lanthanide trichlorides can generally be prepared by dissolving the oxide or carbonate with hydrochloric acid. They are produced commercially by carbothermic reaction of the oxide. To produce the anhydrous forms of these trichlorides, the ammonium chloride route is taken. The anhydrous lanthanide trichlorides have high melting points and are generally pale colored.
| MCl3 | color | structure type | f-configuration | hydrate[5] | THF complexes |
|---|---|---|---|---|---|
| LaCl3 | colorless | UCl3-type | f0 | [LaCl(H2O)7]2Cl4 | [LaCl3(thf)2] = [La(μ-Cl)3(thf)2]n[6] |
| CeCl3 | colorless | UCl3-type | f1, doublet | [CeCl(H2O)7]2Cl4 | [CeCl3(thf)2] = [Ce(μ-Cl)2Cl(thf)2]n[6] |
| PrCl3 | green | UCl3-type | f2, triplet | [PrCl2(H2O)6]Cl | [PrCl3(thf)2] = [Pr(μ-Cl)2Cl(thf)2]n[6] |
| NdCl3 | pink | UCl3-type | f3, quartet | [NdCl2(H2O)6]Cl | [NdCl3(thf)4][7] |
| PmCl3 | green | UCl3-type | f4, quintet | ||
| SmCl3 | yellow | UCl3-type | f5, sextet | [SmCl2(H2O)6]Cl | [SmCl3(thf)4][8] |
| EuCl3 | yellow | UCl3-type | f6, septet | [EuCl2(H2O)6]Cl | |
| GdCl3 | colorless | UCl3-type | f7, octet | [GdCl2(H2O)6]Cl | [GdCl3(thf)3·5 = [GdCl2(thf)5]+[GdCl4(thf)2]-[6] |
| TbCl3 | white | PuBr3-type | f8, septet | [TbCl2(H2O)6]Cl | [TbCl3(thf)3·5 = [TbCl2(thf)5]+[TbCl4(thf)2]-[9] |
| DyCl3 | white | AlCl3-type | f9, sextet | [DyCl2(H2O)6]Cl | [DyCl3(thf)3·5 = [DyCl2(thf)5]+[DyCl4(thf)2]-[10] |
| HoCl3 | yellow | AlCl3-type | f10, quintet | [HoCl2(H2O)6]Cl | |
| ErCl3 | violet | AlCl3-type | f11, quartet | [ErCl2(H2O)6]Cl | [ErCl3(thf)3·5 = [ErCl2(thf)5]+[ErCl4(thf)2]-[6] |
| TmCl3 | yellow | AlCl3-type | f12, triplet | [ThCl2(H2O)6]Cl | |
| YbCl3 | colorless | YCl3-type | f13, doublet | [YbCl2(H2O)6]Cl | [YbCl3(thf)3·5 = [YbCl2(thf)5]+[YbCl4(thf)2]-[11] |
| LuCl3 | colorless | AlCl3-type | f14 | [LuCl2(H2O)6]Cl |
See also
References
- ↑ Rossmainth, Kurt (1979-01-01). "Herstellung der klassischen Seltenerd(II)-chloride in Lösung". Anorganische, Struktur- und Physikalische Chemie 110 (4): 109–114. doi:10.1007/BF00903752.
- ↑ Gerd Meyer, Lester R. Morss (1991). Synthesis of lanthanide and actinide compounds. Springer. p. 161. ISBN 0-7923-1018-7. https://books.google.com/books?id=bnS5elHL2w8C&pg=PA161.
- ↑ Brauer, Georg; Baudler, Marianne (1975). Handbuch der Präparativen Anorganischen Chemie, Band I. (3rd ed.). Stuttgart: Ferdinand Enke. ISBN 3-432-02328-6.
- ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
- ↑ Kandabadage, Thimira; Legnon, Beau; Baranets, Sviatoslav (2024). "Comprehensive structural study of lanthanide(III) chloride hydrates: [ RECl3·xH2O (RE = La–Nd, Sm–Lu; x = 6, 7)]". Acta Crystallographica Section e Crystallographic Communications 80 (12): 1342–1349. doi:10.1107/S2056989024011319. PMID 39906789.
- ↑ 6.0 6.1 6.2 6.3 6.4 Deacon, Glen B.; Feng, Tiecheng; Junk, Peter C.; Skelton, Brian W.; Sobolev, Alexander N.; White, Allan H. (1998). "Preparation and X-Ray Crystal Structures of Tetrahydrofuran-Complexed Rare Earth Chlorides — a Structurally Rich Series". Australian Journal of Chemistry 51: 75–89. doi:10.1071/C97174.
- ↑ Wenqi, Chen; Zhongsheng, Jin; Yan, Xing; Yuguo, Fan; Guangdi, Yang (1987). "Crystal structure of NdCl3·4THF and its catalytic activity in polymerization of diene". Inorganica Chimica Acta 130: 125–129. doi:10.1016/S0020-1693(00)85941-1.
- ↑ Anfang, S.; Karl, M.; Faza, N.; Massa, W.; Dehnicke, K.; Magull, J. (1997). "Synthese und Kristallstrukturen der Seltenerd-Komplexe [LaI2(THF)5]+I3−, [SmCl3(THF)4], [ErCl2(THF)5]+ [ErCl4(THF)2]−, [ErCl3(DME)2] und [Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]−". Zeitschrift für Anorganische und Allgemeine Chemie 623 (9): 1425–1432. doi:10.1002/zaac.19976230918.
- ↑ Evans, William J.; Shreeve, Julie L.; Ziller, Joseph W.; Doedens, Robert J. (1995). "Structural Diversity in Solvated Lanthanide Halide Complexes". Inorganic Chemistry 34 (3): 576–585. doi:10.1021/ic00107a009.
- ↑ Barbosa, Guilherme A.; Carneiro Neto, José Severiano; Stoeberl, Bruno J.; Wisbeck, Sarita; Giese, Siddhartha O. K.; Yokaichiya, Fabiano; Costa, Daniel da S.; Barison, Andersson et al. (2025). "High-yield synthesis of heavy rare earth(III) anhydrous solvates: Known, new, and unexpected products". Dalton Transactions 54 (20): 8251–8269. doi:10.1039/D5DT00254K. PMID 40191991.
- ↑ Deacon, Glen B.; Evans, David J.; Junk, Peter C. (2002). "New Variations on the LnCl3(L)n (L = tetrahydrofuran or 1, 2-dimethoxyethane) Structural Theme — NdCl3(dme)2 and YbCl3(THF)3.5". Zeitschrift für Anorganische und Allgemeine Chemie 628 (9–10): 2033–2036. doi:10.1002/1521-3749(200209)628:9/10<2033::AID-ZAAC2033>3.0.CO;2-G.
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