Molybdenum(II) chloride

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Molybdenum(II) chloride
Mo6Cl12-xtal-1993-CM-3D-balls.png
Names
IUPAC names
dichloromolybdenum
dodecachlorohexamolybdenum(II)
Other names
molybdenum(II) chloride, molybdenum dichloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.417 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
  • 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
  • Cl[Mo]Cl
Properties
Cl12Mo6
Appearanceyellow crystalline solid
Density 3.17 g/cm3
Melting point 530 °C (986 °F; 803 K)
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).

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.

Contents

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 (tba)2Mo6Cl14.jpg
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] Mo6Cl14-anion-from-xtal-2008-CM-3D-ellipsoids.png
Structure of the cluster anion [Mo6Cl14]
.

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]

Related Research Articles

Inorganic chemistry Field of chemistry

Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.

Alkoxide

An alkoxide is the conjugate base of an alcohol and therefore consists of an organic group bonded to a negatively charged oxygen atom. They are written as RO, where R is the organic substituent. Alkoxides are strong bases and, when R is not bulky, good nucleophiles and good ligands. Alkoxides, although generally not stable in protic solvents such as water, occur widely as intermediates in various reactions, including the Williamson ether synthesis. Transition metal alkoxides are widely used for coatings and as catalysts.

Manganese(II) chloride Chemical compound

Manganese(II) chloride is the dichloride salt of manganese, MnCl2. This inorganic chemical exists in the anhydrous form, as well as the dihydrate (MnCl2·2H2O) and tetrahydrate (MnCl2·4H2O), with the tetrahydrate being the most common form. Like many Mn(II) species, these salts are pink, with the paleness of the color being characteristic of transition metal complexes with high spin d5 configurations. It is a paramagnetic salt.

Cobalt(II) chloride Chemical compound

Cobalt(II) chloride is an inorganic compound of cobalt and chlorine, with the formula CoCl
2
. The compound forms several hydrates CoCl
2
nH
2
O
, for n = 1, 2, 6, and 9. Claims of the formation of tri- and tetrahydrates have not been confirmed. The anhydrous form is a blue crystalline solid; the dihydrate is purple and the hexahydrate is pink. Commercial samples are usually the hexahydrate, which is one of the most commonly used cobalt compounds in the lab.

Chromium(III) chloride Chemical compound

Chromium(III) chloride (also called chromic chloride) describes any of several chemical compounds with the formula CrCl3 · xH2O, where x can be 0, 5, and 6. The anhydrous compound with the formula CrCl3 is a violet solid. The most common form of the trichloride is the dark green hexahydrate, CrCl3 · 6 H2O. Chromium chlorides find use as catalysts and as precursors to dyes for wool.

Nickel(II) chloride Chemical compound

Nickel(II) chloride (or just nickel chloride) is the chemical compound NiCl2. The anhydrous salt is yellow, but the more familiar hydrate NiCl2·6H2O is green. Nickel(II) chloride, in various forms, is the most important source of nickel for chemical synthesis. The nickel chlorides are deliquescent, absorbing moisture from the air to form a solution. Nickel salts have been shown to be carcinogenic to the lungs and nasal passages in cases of long-term inhalation exposure.

Octahedral molecular geometry Molecular geometry

In chemistry, octahedral molecular geometry describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The octahedron has eight faces, hence the prefix octa. The octahedron is one of the Platonic solids, although octahedral molecules typically have an atom in their centre and no bonds between the ligand atoms. A perfect octahedron belongs to the point group Oh. Examples of octahedral compounds are sulfur hexafluoride SF6 and molybdenum hexacarbonyl Mo(CO)6. The term "octahedral" is used somewhat loosely by chemists, focusing on the geometry of the bonds to the central atom and not considering differences among the ligands themselves. For example, [Co(NH3)6]3+, which is not octahedral in the mathematical sense due to the orientation of the N−H bonds, is referred to as octahedral.

Chalcogenide

A chalcogenide is a chemical compound consisting of at least one chalcogen anion and at least one more electropositive element. Although all group 16 elements of the periodic table are defined as chalcogens, the term chalcogenide is more commonly reserved for sulfides, selenides, tellurides, and polonides, rather than oxides. Many metal ores exist as chalcogenides. Photoconductive chalcogenide glasses are used in xerography. Some pigments and catalysts are also based on chalcogenides. The metal dichalcogenide MoS2 is a common solid lubricant.

Octahedral clusters are inorganic or organometallic cluster compounds composed of six metals in an octahedral array. Many types of compounds are known, but all are synthetic.

Tantalum(V) chloride Chemical compound

Tantalum(V) chloride, also known as tantalum pentachloride, is an inorganic compound with the formula TaCl5. It takes the form of a white powder and is commonly used as a starting material in tantalum chemistry. It readily hydrolyzes to form tantalum(V) oxychloride (TaOCl3) and eventually tantalum pentoxide (Ta2O5); this requires that it be synthesised and manipulated under anhydrous conditions, using air-free techniques.

Hafnium tetrachloride Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

Vanadium tetrachloride is the inorganic compound with the formula VCl4. This bright red liquid serves as a useful reagent for the preparation of other vanadium compounds.

Molybdenum(V) chloride Chemical compound

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.

Nitrosyl chloride Chemical compound

Nitrosyl chloride is the chemical compound with the formula NOCl. It is a yellow gas that is commonly encountered as a component of aqua regia, a mixture of 3 parts concentrated hydrochloric acid and 1 part of concentrated nitric acid. It is a strong electrophile and oxidizing agent. It is sometimes called Tilden's reagent, after William A. Tilden, who was the first to produce it as a pure compound.

Molybdenum tetrachloride Chemical compound

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.

Organomolybdenum chemistry

Organomolybdenum chemistry is the chemistry of chemical compounds with Mo-C bonds. The heavier group 6 elements molybdenum and tungsten form organometallic compounds similar to those in organochromium chemistry but higher oxidation states tend to be more common.

Pentaamine(dinitrogen)ruthenium(II) chloride Chemical compound

Pentaamine(nitrogen)ruthenium(II) chloride is an inorganic compound with the formula [Ru(NH3)5(N2)]Cl2. It is a nearly white solid, but its solutions are yellow. The cationic complex is of historic significance as the first compound with N2 bound to a metal center. [Ru(NH3)5(N2)]2+ adopts an octahedral structure with C4v symmetry.

In chemistry, aluminium(I) refers to monovalent aluminium in both ionic and covalent bonds. Along with aluminium(II), it is an extremely unstable form of aluminium.

Metal cluster compound Cluster of three or more metals

Metal cluster compounds are a molecular ion or neutral compound composed of three or more metals and featuring significant metal-metal interactions.

Transition metal chloride complex Coordination complex

In chemistry, a transition metal chloride complex is a coordination complex that consists of a transition metal coordinated to one or more chloride ligand. The class of complexes is extensive.

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. Vol. 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. Vol. 44. pp. 45–91. doi:10.1016/S0898-8838(08)60128-2. ISBN   9780120236442.