Molybdenum hexacarbonyl

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Molybdenum hexacarbonyl
Stereo, skeletal formula of molybdenum hexacarbonyl Molybdenum-hexacarbonyl-2D.png
Stereo, skeletal formula of molybdenum hexacarbonyl
Ball and stick model of molybdenum hexacarbonyl Molybdenum-hexacarbonyl-from-xtal-3D-balls.png
Ball and stick model of molybdenum hexacarbonyl
Mocarbonyl.JPG
Names
IUPAC name
Hexacarbonylmolybdenum(0)
Systematic IUPAC name
Hexacarbonylmolybdenum [1]
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.034.271 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 237-713-3
3798, 562210
MeSH Hexacarbonylmolybdenum
PubChem CID
UN number 3466
  • InChI=1S/6CO.Mo/c6*1-2; X mark.svgN
    Key: KMKBZNSIJQWHJA-UHFFFAOYSA-N X mark.svgN
  • O=C=[Mo](=C=O)(=C=O)(=C=O)(=C=O)=C=O
Properties
C6MoO6
Molar mass 264.01 g·mol−1
AppearanceVivid, white, translucent crystals
Density 1.96 g cm−3
Melting point 150 °C (302 °F; 423 K)
Boiling point 156 °C (313 °F; 429 K)
insoluble
Solubility slightly soluble in THF, diglyme, acetonitrile [2]
Structure
Orthogonal
Octahedral
0 D
Thermochemistry
−989.1 kJ mol−1
−2123.4 kJ mol−1
Hazards
GHS labelling:
GHS-pictogram-skull.svg
Danger
H300, H310, H315, H319, H330, H413
P261, P271, P280, P304+P340+P311, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
4
1
0
Safety data sheet (SDS) External MSDS
Related compounds
Related compounds
Chromium hexacarbonyl


Tungsten hexacarbonyl
Seaborgium hexacarbonyl [3]

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Molybdenum hexacarbonyl (also called molybdenum carbonyl) is the chemical compound with the formula Mo(CO)6. This colorless solid, like its chromium, tungsten, and seaborgium analogues, is noteworthy as a volatile, air-stable derivative of a metal in its zero oxidation state.

Contents

Structure and properties

Mo(CO)6 adopts an octahedral geometry consisting of six rod-like CO ligands radiating from the central Mo atom. A recurring minor debate in some chemical circles concerns the definition of an "organometallic" compound. Usually, organometallic indicates the presence of a metal directly bonded via a M–C bond to an organic fragment, which must in turn have a C–H bond.

Like many metal carbonyls, Mo(CO)6 is generally prepared by "reductive carbonylation", which involves reduction of a metal halide with under an atmosphere of carbon monoxide. As described in a 2023 survey of methods "most cost-effective routes for the synthesis of group 6 hexacarbonyls are based on the reduction of the metal chlorides (CrCl3, MoCl5 or WCl6) with magnesium, zinc or aluminium powders... under CO pressures". [4]

Occurrence

Mo(CO)6 has been detected in landfills and sewage plants, the reducing, anaerobic environment being conducive to formation of Mo(CO)6. [5]

Inorganic and organometallic research

Molybdenum hexacarbonyl is a popular reagent in academic research. [6]

One or more CO ligands can be displaced by other ligands. [7] Mo(CO)6, [Mo(CO)3(MeCN)3], and related derivatives are employed as catalysts in organic synthesis for example, alkyne metathesis and the Pauson–Khand reaction.

Mo(CO)6 reacts with 2,2′-bipyridine to afford Mo(CO)4(bipy). UV-photolysis of a THF solution of Mo(CO)6 gives Mo(CO)5(THF).

[Mo(CO)4(piperidine)2]

The thermal reaction of Mo(CO)6 with piperidine affords Mo(CO)4(piperidine)2. The two piperidine ligands in this yellow-colored compound are labile, which allows other ligands to be introduced under mild conditions. For instance, the reaction of [Mo(CO)4(piperidine)2] with triphenyl phosphine in boiling dichloromethane (b.p. ca. 40 °C) gives cis-[Mo(CO)4(PPh3)2]. This cis- complex isomerizes in toluene to trans-[Mo(CO)4(PPh3)2]. [8]

[Mo(CO)3(MeCN)3]

Mo(CO)6 also can be converted to its tris(acetonitrile) derivative. The compound serves as a source of "Mo(CO)3". For instance treatment with allyl chloride gives [MoCl(allyl)(CO)2(MeCN)2], whereas treatment with KTp and sodium cyclopentadienide gives [MoTp(CO)3] and [MoCp(CO)3] anions, respectively. These anions react with a variety of electrophiles. [9] A related source of Mo(CO)3 is cycloheptatrienemolybdenum tricarbonyl.

Source of Mo atoms

Molybdenum hexacarbonyl is widely used in electron beam-induced deposition technique - it is easily vaporized and decomposed by the electron beam providing a convenient source of molybdenum atoms. [10]

Safety and handling

Like all metal carbonyls, Mo(CO)6 is a dangerous source of volatile metal as well as CO.

Related Research Articles

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<span class="mw-page-title-main">Wilkinson's catalyst</span> Chemical compound

Wilkinson's catalyst is the common name for chlorido­tris(triphenylphosphine)­rhodium(I), a coordination complex of rhodium with the formula [RhCl(PPh3)3], where 'Ph' denotes a phenyl group). It is a red-brown colored solid that is soluble in hydrocarbon solvents such as benzene, and more so in tetrahydrofuran or chlorinated solvents such as dichloromethane. The compound is widely used as a catalyst for hydrogenation of alkenes. It is named after chemist and Nobel laureate Sir Geoffrey Wilkinson, who first popularized its use.

<span class="mw-page-title-main">Triphenylphosphine</span> Chemical compound

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

<span class="mw-page-title-main">Chromium hexacarbonyl</span> Chemical compound

Chromium hexacarbonyl (IUPAC name: hexacarbonylchromium) is a chromium(0) organometallic compound with the formula Cr(CO)6. It is homoleptic complex, which means that all the ligands are identical. It is a white, air-stable solid with a high vapor pressure.

<span class="mw-page-title-main">Metal carbonyl</span> Coordination complexes of transition metals with carbon monoxide ligands

Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry. In the Mond process, nickel tetracarbonyl is used to produce pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometallic complexes.

<span class="mw-page-title-main">Dicobalt octacarbonyl</span> Chemical compound

Dicobalt octacarbonyl is an organocobalt compound with composition Co2(CO)8. This metal carbonyl is used as a reagent and catalyst in organometallic chemistry and organic synthesis, and is central to much known organocobalt chemistry. It is the parent member of a family of hydroformylation catalysts. Each molecule consists of two cobalt atoms bound to eight carbon monoxide ligands, although multiple structural isomers are known. Some of the carbonyl ligands are labile.

<span class="mw-page-title-main">Tungsten hexacarbonyl</span> Chemical compound

Tungsten hexacarbonyl (also called tungsten carbonyl) is an organometallic compound with the formula W(CO)6. This complex gave rise to the first example of a dihydrogen complex.

<span class="mw-page-title-main">Organotitanium chemistry</span>

Organotitanium chemistry is the science of organotitanium compounds describing their physical properties, synthesis, and reactions. Organotitanium compounds in organometallic chemistry contain carbon-titanium chemical bonds. They are reagents in organic chemistry and are involved in major industrial processes.

<span class="mw-page-title-main">Organoiridium chemistry</span> Chemistry of organometallic compounds containing an iridium-carbon bond

Organoiridium chemistry is the chemistry of organometallic compounds containing an iridium-carbon chemical bond. Organoiridium compounds are relevant to many important processes including olefin hydrogenation and the industrial synthesis of acetic acid. They are also of great academic interest because of the diversity of the reactions and their relevance to the synthesis of fine chemicals.

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<span class="mw-page-title-main">Organorhodium chemistry</span> Field of study

Organorhodium chemistry is the chemistry of organometallic compounds containing a rhodium-carbon chemical bond, and the study of rhodium and rhodium compounds as catalysts in organic reactions.

<span class="mw-page-title-main">Organomolybdenum chemistry</span> Chemistry of compounds with Mo-C bonds

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.

<span class="mw-page-title-main">Molybdenum(II) acetate</span> Chemical compound

Molybdenum(II) acetate is a coordination compound with the formula Mo2(O2CCH3)4. It is a yellow, diamagnetic, air-stable solid that is slightly soluble in organic solvents. Molybdenum(II) acetate is an iconic example of a compound with a metal-metal quadruple bond.

<span class="mw-page-title-main">Iron tetracarbonyl dihydride</span> Chemical compound

Iron tetracarbonyl dihydride is the organometallic compound with the formula H2Fe(CO)4. This compound was the first transition metal hydride discovered. The complex is stable at low temperatures but decomposes rapidly at temperatures above –20 °C.

<span class="mw-page-title-main">(Mesitylene)molybdenum tricarbonyl</span> Chemical compound

(Mesitylene)molybdenum tricarbonyl is an organomolybdenum compound derived from the aromatic compound mesitylene (1,3,5-trimethylbenzene) and molybdenum carbonyl. It exists as pale yellow crystals, which are soluble in organic solvents but decompose when in solution. It has been examined as a catalyst and reagent.

<span class="mw-page-title-main">Cyclopentadienyliron dicarbonyl dimer</span> Chemical compound

Cyclopentadienyliron dicarbonyl dimer is an organometallic compound with the formula [(η5-C5H5)Fe(CO)2]2, often abbreviated to Cp2Fe2(CO)4, [CpFe(CO)2]2 or even Fp2, with the colloquial name "fip dimer". It is a dark reddish-purple crystalline solid, which is readily soluble in moderately polar organic solvents such as chloroform and pyridine, but less soluble in carbon tetrachloride and carbon disulfide. Cp2Fe2(CO)4 is insoluble in but stable toward water. Cp2Fe2(CO)4 is reasonably stable to storage under air and serves as a convenient starting material for accessing other Fp (CpFe(CO)2) derivatives (described below).

<span class="mw-page-title-main">Half sandwich compound</span> Class of coordination compounds

Half sandwich compounds, also known as piano stool complexes, are organometallic complexes that feature a cyclic polyhapto ligand bound to an MLn center, where L is a unidentate ligand. Thousands of such complexes are known. Well-known examples include cyclobutadieneiron tricarbonyl and (C5H5)TiCl3. Commercially useful examples include (C5H5)Co(CO)2, which is used in the synthesis of substituted pyridines, and methylcyclopentadienyl manganese tricarbonyl, an antiknock agent in petrol.

In organometallic chemistry, a transition metal alkyne complex is a coordination compound containing one or more alkyne ligands. Such compounds are intermediates in many catalytic reactions that convert alkynes to other organic products, e.g. hydrogenation and trimerization.

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<span class="mw-page-title-main">Seaborgium hexacarbonyl</span> Chemical compound

Seaborgium hexacarbonyl (also called seaborgium carbonyl) is the organometallic compound with the formula Sg(CO)6. Like its chromium, molybdenum, and tungsten analogs, it is a volatile derivative of seaborgium in its zero oxidation state. Seaborgium hexacarbonyl has little practical usage, outside of scientific interest, where it and other transactinide compounds are studied to shed light on relativistic effects on electronic structure as a consequence of high nuclear charge.

References

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  2. Faller, John W.; Brummond, Kay M.; Mitasev, Branko (15 September 2006). "Hexacarbonylmolybdenum". Encyclopedia of Reagents for Organic Synthesis. Wiley. doi:10.1002/047084289X. hdl:10261/236866. ISBN   9780470842898.
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  4. Bruno, Sofia M.; Valente, Anabela A.; Gonçalves, Isabel S.; Pillinger, Martyn (2023). "Group 6 Carbonyl Complexes of N,O,P-Ligands as Precursors of High-Valent Metal-Oxo Catalysts for Olefin Epoxidation". Coordination Chemistry Reviews. 478: 214983. doi: 10.1016/j.ccr.2022.214983 . S2CID   255329673.
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  9. Elschenbroich, C.; Salzer, A. (1992). Organometallics: A Concise Introduction (2nd ed.). Weinheim: Wiley-VCH. ISBN   3-527-28165-7.
  10. Randolph, S. J.; Fowlkes, J. D.; Rack, P. D. (2006). "Focused, Nanoscale Electron-Beam-Induced Deposition and Etching". Critical Reviews of Solid State and Materials Sciences. 31 (3): 55–89. Bibcode:2006CRSSM..31...55R. doi:10.1080/10408430600930438. S2CID   93769658.

Further reading