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Molybdenum tetrachloride

Molybdenum tetrachloride

| NFPA-H = 3 | NFPA-F = 0 | NFPA-R = 1 | NFPA-S = Molybdenum(III) chloride Molybdenum(V) chloride Molybdenum tetrachloride is the inorganic compound with the empirical formula MoCl4. The material exists as two polymorphs, both being dark-colored paramagnetic solids. These compounds are mainly of interest as precursors to other molybdenum complexes.

Structure

Structure of β-MoCl4

The α polymorph is a polymer. The β polymorph is a hexamer. In both polymorph, the Mo center is octahedral with two terminal chloride ligands and four doubly bridging ligands. In addition to these two binary phases, a number of adducts are known with the formula where L is a Lewis base.

Preparation

α-Molybdenum tetrachloride can be prepared from by dechlorination of molybdenum pentachloride using tetrachloroethene: : 2MoCl5 + C2Cl4 → 2MoCl4 + C2Cl6

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

Reactions

When heated in an open container, molybdenum tetrachloride evolves chlorine, giving molybdenum trichloride; : 2MoCl4 → 2MoCl3 + Cl2

The acetonitrile complex adduct can be prepared by reduction of the pentachloride with acetonitrile: : 2MoCl5 + 5CH3CN → 2MoCl4(CH3CN)2 + ClCH2CN + HCl The MeCN ligands can be exchanged with other ligands: : MoCl4(CH3CN)2 + 2THF → MoCl4(THF)2 + 2CH3CN

The pentachloride can be reduced to the ether complex MoCl4(Et2O)2 using tin powder. It is a beige, paramagnetic solid.

References

References

  1. Ulrich Müller. (1981). "Hexameric Molybdenum Tetrachloride". Angewandte Chemie International Edition in English.
  2. (1970). "Inorganic Syntheses".
  3. (2014). "Inorganic Syntheses: Volume 36".
  4. (1990). "Inorganic Syntheses".
  5. (2014). "Inorganic Syntheses: Volume 36".
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chlorides molybdenum-halides molybdenum(iv)-compounds
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