Chemistry:Neodymium(II) iodide

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Neodymium(II) iodide
Strontium-bromide-xtal-2011-Mercury-3D-balls.png
Names
IUPAC name
Diiodoneodymium
Other names
Neodymium diiodide
Identifiers
3D model (JSmol)
EC Number
  • 622-142-8
Properties
NdI2
Molar mass 398.05
Appearance dark violet solid[1]
Structure[2]
SrBr2 type (Tetragonal)
P4/n (No. 85)
a = 1257.3 pm, c = 765.8 pm
10
Hazards
GHS pictograms GHS07: Harmful[3]
GHS Signal word Warning[3]
Related compounds
Other anions
Neodymium(II) fluoride, Neodymium(II) chloride, Neodymium(II) bromide
Other cations
lanthanum diiodide, cerium diiodide, praseodymium diiodide, europium diiodide, samarium(II) iodide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Neodymium(II) iodide or neodymium diiodide is an inorganic salt of iodine and neodymium the formula NdI2. Neodymium uses the +2 oxidation state in the compound.

Neodymium(II) iodide is a violet solid.[1] The compound is not stoichiometric.[4] It melts at 562°C.[5]

Preparation

Neodymium(II) iodide can be made by heating molten neodymium(III) iodide with neodymium metal at 800 and 580°C for 12 hours.[4] It can also be obtained by reducing neodymium(III) iodide with neodymium in a vacuum at 800 to 900°C:[1]

Nd + 2NdI3 → 3NdI2

The reaction of neodymium with mercury(II) iodide is also possible because neodymium is more reactive than mercury:[1]

Nd + HgI2 → NdI2 + Hg

Direct preparation from iodine and neodymium is also possible:[6]

Nd + I2 → NdI2

The compound was first synthesized by John D. Corbett in 1961.[7]

Properties

Neodymium(II) iodide is a violet solid.[1] The compound is extremely hygroscopic, and can only be stored and handled under carefully dried inert gas or under a high vacuum.[8] In air it converts into hydrates by absorbing moisture, but these are unstable and more or less rapidly transform into oxide iodides with the evolution of hydrogen:

2NdI2 + 2H2O → 2NdOI + H2↑ + 2HI

Neodymium(II) iodide is not stoichiometric, and has a formula of closer to NdI1.95.[4] It melts at 562°C.[5] It has a strontium(II) bromide-type crystal structure.[1] Under pressure, this transforms into the molybdenum disilicide structure typically seen in intermetallic compound, which is already present under normal conditions in other rare earth diiodides (e.g. praseodymium(II) iodide and lanthanum(II) iodide).[9] It forms complexes with tetrahydrofuran and other organic compounds.[10][11][12]

Neodymium(II) iodide is an electrical insulator.[4]

Reactions

Neodymium(II) iodide reacts with organohalides by extracting the halogen, resulting in dimers, oligomers or reactions with the solvent.[12]

Solvates are known with tetrahydrofuran and dimethoxyethane: NdI2(THF)2 and NdI2(DME)2.[13]

Neodymium(II) iodide reduces hot nitrogen to form an iodide nitride: (NdI2)3N which with THF also gives (NdI)3N2.[14]

It reacts with cyclopentadiene in THF to give CpNdI2(THF)3.[15]

Applications

Neodymium(II) iodide can be used as a reducing agent or catalyst[16] in organic chemistry.[17]

See also

References

  1. 1.0 1.1 1.2 1.3 1.4 1.5 (in de) Handbuch der präparativen anorganischen Chemie. Stuttgart: Enke. 1975. p. 1081. ISBN 3-432-02328-6. OCLC 310719485. 
  2. Beck, H. P. (1976-11-01). "Notizen: NdI2-II, eine metallisch leitende Hochdruckmodifikation ? / NdI2, a Metallic High Pressure Modification ?" (in de). Zeitschrift für Naturforschung B (Walter de Gruyter GmbH) 31 (11): 1548–1549. doi:10.1515/znb-1976-1128. ISSN 1865-7117. 
  3. 3.0 3.1 See https://pubchem.ncbi.nlm.nih.gov/compound/Neodymium_II_-iodide
  4. 4.0 4.1 4.2 4.3 Sallach, Robert A.; Corbett, John D. (July 1964). "Magnetic Susceptibilities of Neodymium (II) Chloride and Iodide". Inorganic Chemistry 3 (7): 993–995. doi:10.1021/ic50017a015. 
  5. 5.0 5.1 Druding, Leonard F.; Corbett, John D. (June 1961). "Lower Oxidation States of the Lanthanides. Neodymium(II) Chloride and Iodide 1". Journal of the American Chemical Society 83 (11): 2462–2467. doi:10.1021/ja01472a010. 
  6. Karl A. Jr. Gschneidner, Jean-Claude Bunzli, Vitalij K. Pecharsky (2009). Handbook on the Physics and Chemistry of Rare Earths. Elsevier. p. 247. ISBN 978-008093257-6. https://books.google.com/books?id=CV-YrFC8_YIC&pg=PA247. 
  7. Angelika Jungmann, R. Claessen, R. Zimmermann, G. e. Meng, P. Steiner, S. Hüfner, S. Tratzky, K. Stöwe, H. P. Beck: Photoemission of LaI2 and CeI2. In: Zeitschrift für Physik B Condensed Matter. 97, 1995, S. 25–34, doi:10.1007/BF01317584.
  8. 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. 
  9. Ralf Alsfasser, Erwin Riedel (2007). Moderne Anorganische Chemie. Walter de Gruyter. p. 188. ISBN 978-311019060-1. https://books.google.com/books?id=HwY4be5bH_sC&pg=PA188. 
  10. Mikhail N. Bochkarev, Igor L. Fedushkin, Sebastian Dechert, Anatolii A. Fagin, Herbert Schumann: [NdI2(thf)5], der erste kristallographisch charakterisierte Neodym(II)-Komplex. In: Angewandte Chemie. 113, 2001, S. 3268–3270, doi:10.1002/1521-3757(20010903)113:17<3268::AID-ANGE3268>3.0.CO;2-K.
  11. G. V. Khoroshen kov, A. A. Fagin, M. N. Bochkarev, S. Dechert, H. Schumann: Reactions of neodymium(II), dysprosium(II), and thulium(II) diiodides with cyclopentadiene In: Russian Chemical Bulletin. 52, S. 1715–1719, doi:10.1023/A:1026132017155.
  12. 12.0 12.1 Fagin, Anatolii A.; Balashova, Tatyana V.; Kusyaev, Dmitrii M. et al. (March 2006). "Reactions of neodymium(II) iodide with organohalides". Polyhedron 25 (5): 1105–1110. doi:10.1016/j.poly.2005.08.050. 
  13. Bochkarev, Mikhail N.; Fagin, Anatolii A. (24 September 1999). "A New Route to Neodymium(II) and Dysprosium(II) Iodides". Chemistry - A European Journal 5 (10): 2990–2992. doi:10.1002/(SICI)1521-3765(19991001)5:10<2990::AID-CHEM2990>3.0.CO;2-U. 
  14. Fagin, A. A.; Salmova, S. V.; Bochkarev, M. N. (January 2009). "Reduction of nitrogen with neodymium(II) and dysprosium(II) diiodides and selected properties of the resulting nitrides". Russian Chemical Bulletin 58 (1): 230–233. doi:10.1007/s11172-009-0034-2. 
  15. Khoroshen'kov, G. V.; Fag, A. A.; Bochkarev, M. N.; Dechert, S.; Schumann, H. (1 August 2003). "Reactions of neodymium(ii), dysprosium(ii), and thulium(ii) diiodides with cyclopentadiene. Molecular structures of complexes CpTmI2(THF)3 and [NdI2(THF)5]+[NdI4(THF)2]–". Russian Chemical Bulletin 52 (8): 1715–1719. doi:10.1023/A:1026132017155. 
  16. Fundamental Chemistry (2006). Neodymium Based Ziegler Catalysts. Springer. p. 13. ISBN 354034809-3. https://books.google.com/books?id=xX9mYOp2HFYC&pg=PA13. 
  17. Handbook on the Physics and Chemistry of Rare Earths. Elsevier. 2009. p. 261. ISBN 978-008093257-6. https://books.google.com/books?id=CV-YrFC8_YIC&pg=PA261. 
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