Molybdenum tetrachloride

Molybdenum tetrachloride is the inorganic compound with the empirical formula MoCl4. The material exists as two polymorphs, a polymeric ("α") and a hexameric ("β") structure. In each polymorph, the Mo center is octahedral with two terminal chloride ligands and four doubly bridging ligands.[1]

Molybdenum tetrachloride
Names
IUPAC name
Molybdenum tetrachloride
Other names
Molybdenum(IV) chloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.039
UNII
Properties
Cl4Mo
Molar mass 237.752 g/mol
Appearance black solid
Melting point 552 °C (1,026 °F; 825 K)
Decomposes
Hazards
NFPA 704 (fire diamond)
Flammability code 0: Will not burn. E.g. waterHealth code 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasReactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
0
3
1
Flash point Non flammable
Related compounds
Related compounds
Molybdenum(II) chloride
Molybdenum(III) chloride
Molybdenum(V) chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

Preparation

α-Molybdenum tetrachloride can be prepared from by dechlorination of molybdenum pentachloride using tetrachloroethene:[2]

2 MoCl5 + C2Cl4 → 2 MoCl4 + C2Cl6

Heating α-molybdenum tetrachloride in a sealed container in the presence of molybdenum pentachloride induces conversion to the β polymorph.[2]

Reactions

When heated in an open container, molybdenum tetrachloride evolves chlorine, giving molybdenum trichloride;[2]

2 MoCl4 → 2 MoCl3 + Cl2

The acetonitrile complex adduct can be prepared by reduction of the pentachloride with acetonitrile:[3][4]

2 MoCl5 + 5 CH3CN → 2 MoCl4(CH3CN)2 + ClCH2CN + HCl

The MeCN ligands can be exchanged with other ligands:

MoCl4(CH3CN)2 + 2 THF → MoCl4(THF)2 + 2 CH3CN

References

  1. Ulrich Müller (1981). "Hexameric Molybdenum Tetrachloride". Angewandte Chemie International Edition in English. 20: 692. doi:10.1002/anie.198106921.
  2. McCann III, E. L.; Brown, T. M. (1970). "Molybdenum(IV) Chloride". Inorganic Syntheses. 12: 181. doi:10.1002/9780470132432.ch31.
  3. Broderick, Erin M.; Browne, Samuel C.; Johnson, Marc J. A. (2014). "Dimolybdenum and Ditungsten Hexa(Alkoxides)". Inorganic Syntheses. 36: 95–102. doi:10.1002/9781118744994.ch18.
  4. Dilworth, Jonathan R.; Richards, Raymond L. (1990). "The Synthesis of Molybdenum and Tungsten Dinitrogen Complexes". Inorganic Syntheses. 28: 33. doi:10.1002/9780470132593.ch7.
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