Molybdenum(V) chloride

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Molybdenum(V) chloride
Molybdenum(V) chloride
Ball-and-stick model of the Mo2Cl10 molecule in the crystal structure
Names
IUPAC names
Molybdenum(V) chloride
Molybdenum pentachloride
Identifiers
10241-05-1 YesY
ECHA InfoCard 100.030.510
EC Number 233-575-3
PubChem 61497
RTECS number QA4690000
UNII BB0UFP2VO5 N
Properties
Cl10Mo2
Molar mass 273.21 g/mol (MoCl5)
Appearance dark-green solid
hygroscopic
paramagnetic
Density 2.928 g/cm3
Melting point 194 °C (381 °F; 467 K)
Boiling point 268 °C (514 °F; 541 K)
hydrolyzes
Solubility soluble in dry ether, dry alcohol, organic solvents
Structure
monoclinic
edge-shared bioctahedron
Hazards
Main hazards oxidizer, hydrolyzes to release HCl
Flash point Non-flammable
Related compounds
Other anions
Molybdenum(V) fluoride
Molybdenum(IV) bromide
Molybdenum(III) iodide
Other cations
Chromium(IV) chloride
Tungsten(V) chloride
Related molybdenum chlorides
Molybdenum(II) chloride
Molybdenum(III) chloride
Molybdenum(IV) 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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Infobox references

Molybdenum(V) chloride is the inorganic compound with the formula [MoCl5]2. This dark volatile solid is used in research to prepare other molybdenum compounds. it is moisture-sensitive and soluble in chlorinated solvents. Usually called molybdenum pentachloride, it is in fact a dimer with the formula Mo2Cl10.[1]

Structure[edit]

Each molybdenum has local octahedral symmetry and two chlorides bridge between the molybdenum centers.[2] A similar structure is also found for the pentachlorides of W, Nb and Ta.[3] In the gas phase and partly in solution, the dimers partially dissociates to give a monomeric pentahalide.[4] The monomer is paramagnetic, with one unpaired electron per Mo center, reflecting the fact that the formal oxidation state is +5, leaving one valence electron on the metal center.

Preparation and properties[edit]

MoCl5 is prepared by chlorination of Mo metal but also chlorination of MoO3. The unstable hexachloride MoCl6 is not produced in this way.[5]

MoCl5 is a strong oxidant. It is reduced by MeCN to afford an orange complex, MoCl4(MeCN)2, which in turn reacts with THF to give MoCl4(THF)2, a precursor to other molybdenum-containing complexes.[6] MoCl5 is reduced by HBr to form MoBr4. The bromination reaction is conducted in ethylbromide at −50 °C, forming MoBr5 as an intermediate. Upon warming to 20 °C, Br2 is produced and the formal oxidation state of molybdenum changes from +5 to +4. The net transformation is shown in the equation:

2 MoCl5 + 10 HBr → 2 MoBr4 + 10 HCl + Br2

MoBr4 reacts with THF to give the Mo(III) species mer-MoBr3(THF)3.[7]

MoCl5 is a good Lewis acid toward non-oxidizable ligands. It forms an adduct with chloride to form [MoCl6]. In organic synthesis, the compound finds occasional use in chlorinations, deoxygenation, and oxidative coupling reactions.[8]

Safety considerations[edit]

MoCl5 is an aggressive oxidant and readily hydrolyzes to release HCl.

References[edit]

  1. ^ Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego, CA: Academic Press. ISBN 0-12-352651-5. 
  2. ^ Beck, J.; Wolf, F. (1997). "Three New Polymorphic Forms of Molybdenum Pentachloride". Acta Crystallogr. B53: 895–903. doi:10.1107/S0108768197008331. 
  3. ^ Wells, A. E. (1984). Structural Inorganic Chemistry (5th ed.). Oxford: Clarendon Press. 
  4. ^ Brunvoll, J.; Ischenko, A. A.; Spiridonov, V. P.; Strand, T. G. (1984). "Composition and Molecular Structure of Gaseous Molybdenum Pentachloride by Electron Diffraction". Acta Chem. Scand. A38: 115–120. doi:10.3891/acta.chem.scand.38a-0115. 
  5. ^ Tamadon, Farhad; Seppelt, Konrad (2013). "The Elusive Halides VCl5, MoCl6, and ReCl6". Angew. Chem. Int. Ed. 52: 767–769. doi:10.1002/anie.201207552. 
  6. ^ Dilworth, J. R.; Richards, R. L. (1990). "The Synthesis of Molybdenum and Tungsten Dinitrogen Compounds". Inorg. Synth. 28: 33–45. ISBN 0-471-52619-3. 
  7. ^ Calderazzo, F.; Maichle-Mössmer, C.; Pampaloni, G.; Strähle, J. (1993). "Low-temperature Syntheses of Vanadium(III) and Molybdenum(IV) Bromides by Halide Exchange". Dalton Trans. 1993: 655–658. doi:10.1039/DT9930000655. 
  8. ^ Kauffmann, T.; Torii, S.; Inokuchi, T. (2004). "Molybdenum(V) Chloride". Encyclopedia of Reagents for Organic Synthesis. New York, NY: J. Wiley & Sons. doi:10.1002/047084289.