Molybdenum(II) chloride

Molybdenum dichloride describes chemical compounds with the empirical formula MoCl₂. At least two forms are known, and both have attracted much attention from academic researchers because of the unexpected structures seen for these compounds and the fact that they give rise to hundreds of derivatives. The form discussed here is Mo₆Cl₁₂. The other molybdenum(II) chloride is potassium octachlorodimolybdate.

Molybdenum(II) chloride

Names
IUPAC names dichloromolybdenum dodecachlorohexamolybdenum(II)
Other names molybdenum(II) chloride, molybdenum dichloride
Identifiers
CAS Number	13478-17-6 (MoCl2) 11062-51-4 (Mo6Cl12)
3D model (JSmol)	Interactive image
ChemSpider	75349
ECHA InfoCard	100.033.417
PubChem CID	83514
CompTox Dashboard (EPA)	DTXSID1065502
InChI InChI=1S/2ClH.Mo/h2*1H;/q;;+2/p-2 Key: BQBYSLAFGRVJME-UHFFFAOYSA-L InChI=1/2ClH.Mo/h2*1H;/q;;+2/p-2/rCl2Mo/c1-3-2 Key: BQBYSLAFGRVJME-LYAHSSGUAS
SMILES Cl[Mo]Cl
Properties
Chemical formula	Cl12Mo6
Appearance	yellow crystalline solid
Density	3.17 g/cm^3
Melting point	530 °C (986 °F; 803 K)
Solubility in water	low
Related compounds
Related compounds	Molybdenum(III) 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).
Infobox references

Structure

Rather than adopting a close-packed structure typical of metal dihalides, e.g., cadmium chloride, molybdenum(II) chloride forms a structure based on clusters. Molybdenum(II), which is a rather large ion, prefers to form compounds with metal-metal bonds, i.e. metal clusters. In fact all "lower halides" (i.e. where halide/M ratio is <4) in the "early transition metal series (Ti, V, Cr, Mn triads) do. The species Mo₆Cl₁₂ is polymeric, consisting of cubic Mo₆Cl₈⁴⁺ clusters interconnected by chloride ligands that bridge from cluster to cluster. This material converts readily to salts of the dianion [Mo₆Cl₁₄]²⁻. In this anion, each Mo bears one terminal chloride but is otherwise part of an Mo₆ octahedron embedded inside a cube defined by eight chloride centers. Thus, the coordination environment of each Mo is four triply bridging chloride ligands, four Mo neighbors, and one terminal Cl. The cluster has 24e⁻, four being provided by each Mo²⁺.[1]

Sample of (NBu₄)₂[Mo₆Cl₁₄

]

Synthesis and reactions

Mo₆Cl₁₂ is prepared by the reaction of molybdenum(V) chloride with molybdenum metal:

12 MoCl₅ + 18 Mo → 5 Mo₆Cl₁₂

This reaction proceeds via the intermediacy of MoCl₃ and MoCl₄, which also are reduced by the presence of excess Mo metal. The reaction is conducted in a tube furnace at 600–650 °C.[2]

Once isolated, Mo₆Cl₁₂ undergoes many reactions with retention of the Mo₆¹²⁺ core. Heating in concentrated HCl gives (H₃O)₂[Mo₆Cl₁₄]. The terminal chloride ligands, labeled "ausser" are readily exchanged:

(H₃O)₂[Mo₆Cl₁₄] + 6 HI → (H₃O)₂[Mo₆Cl₈I₆] + 6 HCl

Under more forcing conditions, all 14 ligands can be exchanged, to giving salts of [Mo₆Br₁₄]²⁻ and [Mo₆I₁₄]²⁻.

Structure of the cluster anion [Mo₆Cl₁₄]²⁻

.

Related clusters

Main article: Octahedral cluster

A variety of clusters are structurally related to [Mo₆Cl₁₄]²⁻. The tungsten analogue is known. Ta and Nb form related clusters where halides are bridge edges of the Ta₆ octahedron vs faces. The resulting formula is [Ta₆Cl₁₈]⁴⁻.

Sulfido and selenido derivatives are also well studied. [Re₆Se₈Cl₆]⁴⁻ has the same number of valence electrons as does [Mo₆Cl₁₄]²⁻.[3]

The Mo-S clusters Mo₆S₈L₆, analogues of the "Chevrel phases", have been prepared by the reaction of sulfide sources with Mo₆Cl₁₂ in the presence of donor ligands L.[4]

References

1. von Schnering, H. G.; May, W.; Peters, K. (1993). "Crystal structure of dodecachlorooctahedrohexamolybdenum, Mo₆Cl₁₂". Zeitschrift für Kristallographie. 208 (2): 368–369. Bibcode:1993ZK....208..368V. doi:10.1524/zkri.1993.208.Part-2.368.
2. Larson, Melvin L.; Nannelli, Piero; Block, B. P.; Edwards, D. A.; Mallock, A. K. (2007). "Preparation of Some Metal Halides Anhydrous Molybdenum Halides and Oxide Halides-a Summary: Molybdenum(II) Halides". Inorganic Syntheses. 12. p. 165. doi:10.1002/9780470132432.ch29. ISBN 9780470132432.
3. Lee, Sonny C.; Holm, Richard H. (1990). "Nonmolecular Metal Chalcogenide/Halide Solids and Their Molecular Cluster Analogues". Angewandte Chemie International Edition in English. 29 (8): 840. doi:10.1002/anie.199008401.
4. Saito, Taro (1996). "Group 6 Metal Chalcogenide Cluster Complexes and their Relationships to Solid-State Cluster Compounds". Advances in Inorganic Chemistry. 44. pp. 45–91. doi:10.1016/S0898-8838(08)60128-2. ISBN 9780120236442.