Molybdenum(III) chloride

Molybdenum(III) chloride
Molybdenum(III) chloride alpha polymorph
Molybdenum(III) chloride alpha polymorph
α-MoCl3
Molybdenum(III) chloride beta polymorph
Molybdenum(III) chloride beta polymorph
β-MoCl3
Names
IUPAC names
Molybdenum(III) chloride
Molybdenum trichloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.418 Edit this at Wikidata
EC Number
  • 236-775-9
UNII
  • InChI=1S/3ClH.Mo/h3*1H;/q;;;+3/p-3
    Key: ZSSVQAGPXAAOPV-UHFFFAOYSA-K
  • InChI=1/3ClH.Mo/h3*1H;/q;;;+3/p-3
    Key: ZSSVQAGPXAAOPV-DFZHHIFOAN
  • Cl[Mo](Cl)Cl
Properties
MoCl3
Molar mass 202.30 g/mol
Appearance dark red solid
paramagnetic
Density 3.58 g/cm3
Melting point 410 °C (770 °F; 683 K) (decomposes)
insoluble
Solubility insoluble in ethanol, diethyl ether
+43.0·10−6 cm3/mol
Hazards
Flash point Non-flammable
Related compounds
Other anions
 Molybdenum(III) fluoride
Molybdenum(III) bromide
Molybdenum(III) iodide
Other cations
 Chromium(IV) chloride
Tungsten(V) chloride
Related molybdenum chlorides
 Molybdenum(II) chloride
Molybdenum(IV) chloride
Molybdenum(V) 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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Molybdenum(III) chloride is the inorganic compound with the formula MoCl3. It forms purple crystals.[1]

Synthesis and structure

Molybdenum(III) chloride is synthesized by the reduction of molybdenum(V) chloride with hydrogen.[2] A higher yield is produced by the reduction of pure molybdenum(V) chloride with anhydrous tin(II) chloride as the reducing agent.[3]

Molybdenum trichloride exists as two polymorphs: alpha (α) and beta (β). The alpha structure is similar to that of aluminum chloride (AlCl3). In this structure, molybdenum has octahedral coordination geometry and exhibits cubic close-packing in its crystalline structure. The beta structure, however, exhibits hexagonal close packing.[4]

Ether complexes

Molybdenum trichloride gives a ether complexes MoCl3(thf)3 and MoCl3(Et2O)3. They are beige, paramagnetic solids. Both feature octahedral Mo centers. The diethyl ether complex is synthesized by reducing a Et2O solution of MoCl5 with tin powder.[5] Older procedures involve stepwise reduction involving isolation of the Mo(IV)-thf complex.[6]

Hexa(tert-butoxy)dimolybdenum(III) is prepared by the salt metathesis reaction from MoCl3(thf)3:[7]

2 MoCl3(thf)3 + 6 LiOBu-t → Mo2(OBu-t)6 + 6 LiCl + 6 thf

References

  1. ^ Perry DL (2011). Handbook of Inorganic Compounds (2nd ed.). Boca Raton: Taylor & Francis. p. 279. ISBN 978-1-4398-1461-1.
  2. ^ Couch DE, Brenner A (1959). "Preparation of Trichloride and Tetrachloride of Molybdenum". Journal of Research of the National Bureau of Standards Section A. 63A (2): 185–188. doi:10.6028/jres.063A.013. PMC 5287202. PMID 31216151.
  3. ^ Larson ML (1970). "Preparation of Some Metal Halides- Anhydrous Molybdenum Halides and Oxide Halides - A Summary". Inorganic Syntheses. Vol. 12. pp. 178–181.
  4. ^ Hillebrecht H, Schmidt PJ, Rotter HW, Thiele G, Zönnchen P, Bengel H, Cantow HJ, Magonov SN, Whangbo MH (1997). "Structural and scanning microscopy studies of layered compounds MCl3 (M= Mo, Ru, Cr) and MOCl2 (M= V, Nb, Mo, Ru, Os)". Journal of Alloys and Compounds. 246 (1–2): 70–79. doi:10.1016/S0925-8388(96)02465-6.
  5. ^ Maria, Sébastien; Poli, Rinaldo (2014). "Ether Complexes of Molybdenum(III) and Molybdenum(IV) chlorides". Inorganic Syntheses: Volume 36 (PDF). Inorganic Syntheses. Vol. 36. pp. 15–18. doi:10.1002/9781118744994.ch03. ISBN 9781118744994.
  6. ^ Dilworth, Jonathan R.; Richards, Raymond L. (1990). "The Synthesis of Molybdenum and Tungsten Dinitrogen Complexes". Inorganic Syntheses. Inorganic Syntheses. Vol. 28. pp. 33–43. doi:10.1002/9780470132593.ch7. ISBN 9780470132593.
  7. ^ Broderick, Erin M.; Browne, Samuel C.; Johnson, Marc J. A. (2014). "Dimolybdenum and Ditungsten Hexa(Alkoxides)". Inorganic Syntheses: Volume 36. Inorganic Syntheses. Vol. 36. pp. 95–102. doi:10.1002/9781118744994.ch18. ISBN 9781118744994.