Chemistry:Lanthanum(III) iodide

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Lanthanum(III) iodide
Unit cell of PuBr3.png
Names
Other names
Lanthanum triiodide
Identifiers
3D model (JSmol)
EC Number
  • 237-465-6
Properties
LaI3
Molar mass 519.62
Density 5.63 g/mL at 25 °C
Melting point 772 °C (1,422 °F; 1,045 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Lanthanum(III) iodide is an inorganic compound containing lanthanum and iodine with the chemical formula LaI3.[1]

Synthesis

Lanthanum(III) iodide can be synthesised by the reaction of lanthanum metal with mercury(II) iodide:[2][3]

2 La + 3 HgI2 → 2 LaI3 + 3 Hg

It can also be prepared from the elements, that is by the reaction of metallic lanthanum with iodine:[2]

2 La + 3 I2 → 2 LaI3

While lanthanum(III) iodide solutions can be generated by dissolving lanthanum oxide in hydroiodic acid, the product will hydrolyse and form polymeric hydroxy species:[4]

La2O3 + 6 HI → 2 LaI3 + 3 H2O → further reactions

Structure

Lanthanum(III) iodide adopts the same crystal structure as plutonium(III) bromide, with 8-coordinate metal centres arranged in layers.[4][5] This orthorhombic structure is typical of the triiodides of the lighter lanthanides (La–Nd), whereas heavier lanthanides tend to adopt the hexagonal bismuth(III) iodide structure.[3]

Reactivity and applications

Lanthanum(III) iodide is very soluble in water and is deliquescent.[4] Anhydrous lanthanum(III) iodide reacts with tetrahydrofuran to form a photoluminescent complex, LaI3(THF)4, with an average La–I bond length of 3.16 Å.[6][7] This complex is a starting material for amide and cyclopentadienyl complexes of lanthanum.[6][8]

Related compounds

Lanthanum also forms a diiodide, LaI2. It is an electride and is best formulated {LaIII,2I−,e−}, with the electron delocalised in a conduction band.[4] Several other lanthanides form similar compounds, including CeI2, PrI2 and GdI2.[9] Lanthanum diiodide adopts the same tetragonal crystal structure as PrI2.[10]

Lanthanum(III) iodide reacts with lanthanum metal under an argon atmosphere in a tantalum capsule at 1225 K to form the mixed-valence compound La2I5.[11]

Reduction of LaI2 or LaI3 with metallic sodium in an argon atmosphere at 550 °C gives lanthanum monoiodide, LaI, which has a hexagonal crystal structure.[12]

References

  1. ↑ Taylor, Moddie D. (1962). "Preparation of Anhydrous Lanthanon Halides". Chem. Rev. 62 (6): 503–511. doi:10.1021/cr60220a001. 
  2. ↑ 2.0 2.1 Corbett, John D.; Simon, Arndt (1984). "Chapter 6: Lanthanum Triiodide (and Other Rare Earth Metal Triiodides)". in Holt Jr., Smith L.. Inorg. Synth.. 22. pp. 11–16. doi:10.1002/9780470132531.ch6. 
  3. ↑ 3.0 3.1 Asprey, L. B.; Keenan, T. K.; Kruse, F. H. (1964). "Preparation and Crystal Data for Lanthanide and Actinide Triiodides". Inorg. Chem. 3 (8): 1137–1141. doi:10.1021/ic50018a015. https://digital.library.unt.edu/ark:/67531/metadc867868/. 
  4. ↑ 4.0 4.1 4.2 4.3 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 949–950. ISBN 978-0-08-037941-8. 
  5. ↑ Wells, A. F. (1984). Structural Inorganic Chemistry (5th ed.). Oxford University Press. p. 420. ISBN 978-0-19-965763-6. 
  6. ↑ 6.0 6.1 Ortu, Fabrizio (2022). "Rare Earth Starting Materials and Methodologies for Synthetic Chemistry". Chem. Rev. 122 (6): 6040–6116. doi:10.1021/acs.chemrev.1c00842. PMID 35099940. 
  7. ↑ Li, Yangjuan; Chen, Xiuting; Gong, Yu (2021). "Photoluminescence of LaI3 switched on and off by association and dissociation of non-luminescent tetrahydrofuran". Dalton Trans. 50 (11): 3797–3800. doi:10.1039/D1DT00162K. PMID 33720234. 
  8. ↑ Windorff, Cory J.; Dumas, Megan T.; Ziller, Joseph W.; Gaunt, Andrew J.; Kozimor, Stosh A.; Evans, William J. (2017). "Small-Scale Metal-Based Syntheses of Lanthanide Iodide, Amide, and Cyclopentadienyl Complexes as Analogues for Transuranic Reactions". Inorg. Chem. 56 (19): 11981–11989. doi:10.1021/acs.inorgchem.7b01968. PMID 28915015. 
  9. ↑ Wells, A. F. (1984). Structural Inorganic Chemistry (5th ed.). Oxford University Press. p. 1250. ISBN 978-0-19-965763-6. 
  10. ↑ Burrow, J. H.; Maule, C. H.; Strange, P.; Tothill, J. N.; Wilson, J. A. (1987). "The electronic conditions in the 5d1 layer-metal LaI2 making comparison with the iso-electronic tantalum dichalcogenides, with the other RE di-iodides, and with the RE monochalcogenides". J. Phys. C: Solid State Phys. 20 (26): 4115–4133. doi:10.1088/0022-3719/20/26/014. Bibcode: 1987JPhC...20.4115B. 
  11. ↑ Mattausch, Hj.; Oeckler, O.; Simon, A. (2003). "Crystal structure of dilanthanum pentaiodide, La2I5". Z. Kristallogr. NCS 218 (3): 281. doi:10.1524/ncrs.2003.218.3.281. 
  12. ↑ Ryazanov, Mikhail; Kienle, Lorenz; Simon, Arndt; Mattausch, Hansjürgen (2006). "New Synthesis Route to and Physical Properties of Lanthanum Monoiodide". Inorg. Chem. 45 (5): 2068–2074. doi:10.1021/ic051834r. PMID 16499368. 
HI He
LiI BeI2 BI3 CI4 NI3 I2O4,
I2O5,
I4O9 		IF,
IF3,
IF5,
IF7 		Ne
NaI MgI2 AlI3 SiI4 PI3,
P2I4 		S ICl,
ICl3 		Ar
KI CaI2 Sc TiI4 VI3 CrI3 MnI2 FeI2 CoI2 NiI2 CuI ZnI2 Ga2I6 GeI2,
GeI4 		AsI3 Se IBr Kr
RbI SrI2 YI3 ZrI4 NbI5 Mo Tc Ru Rh Pd AgI CdI2 InI3 SnI4,
SnI2 		SbI3 TeI4 I Xe
CsI BaI2   HfI4 TaI5 W Re Os Ir Pt AuI Hg2I2,
HgI2 		TlI PbI2 BiI3 Po AtI Rn
Fr RaI2   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La Ce Pr Nd Pm SmI2 Eu Gd TbI3 Dy Ho Er Tm Yb Lu
Ac ThI4 Pa UI3,
UI4 		Np Pu Am Cm Bk Cf EsI3 Fm Md No Lr



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