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Molybdenum tetrachloride is the
inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...
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

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 know with the formula where L is a
Lewis base A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...
.


Preparation

α-Molybdenum tetrachloride can be prepared from by dechlorination of
molybdenum pentachloride Molybdenum(V) chloride is the inorganic compound with the empirical formula . This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents. Structure Usually call ...
using
tetrachloroethene Tetrachloroethylene, also known under the systematic name tetrachloroethene, or perchloroethylene, and many other names (and abbreviations such as "perc" or "PERC", and "PCE"), is a chlorocarbon with the formula Cl2C=CCl2 . It is a colorless liq ...
: : 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 Molybdenum(III) chloride is the inorganic compound with the formula MoCl3. It forms purple crystals. Synthesis and structure Molybdenum(III) chloride is synthesized by the reduction of molybdenum(V) chloride with hydrogen. A higher yield is pro ...
; : 2MoCl4 → 2MoCl3 + Cl2 The
acetonitrile complex Transition metal nitrile complexes are coordination compounds containing nitrile ligands. Because nitriles are weakly basic, the nitrile ligands in these complexes are often labile. Scope of nitriles Typical nitrile ligands are acetonitrile, prop ...
adduct can be prepared by reduction of the pentachloride with acetonitrile: : 2MoCl5 + 5CH3CN → 2MoCl4(CH3CN)2 + ClCH2CN + HCl The MeCN
ligand In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electr ...
s can be exchanged with other ligands: : MoCl4(CH3CN)2 + 2
THF Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water- miscible organic liquid with low viscosity. It is ...
→ 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

{{Chlorides Chlorides Molybdenum halides