Molybdenum Carbonyl
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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 hexacarbonyl, chromium, tungsten hexacarbonyl, tungsten, and seaborgium hexacarbonyl, seaborgium analogues, is noteworthy as a volatile, air-stable derivative of a metal in its zero oxidation state.


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".


Occurrence

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


Inorganic and organometallic research

Molybdenum hexacarbonyl is a popular reagent in academic research. One or more CO ligands can be displaced by other ligands. 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-trans isomerism, ''cis''-[Mo(CO)4(PPh3)2]. This ''cis-'' complex isomerizes in toluene to trans isomer, ''trans''-[Mo(CO)4(PPh3)2].


[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 Scorpionate ligand, KTp and sodium cyclopentadienide gives [MoTp(CO)3] and [MoCp(CO)3] anions, respectively. These anions react with a variety of electrophiles. 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.


Safety and handling

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


References


Further reading

* * * {{Molybdenum compounds Molybdenum(0) compounds Carbonyl complexes Organomolybdenum compounds Octahedral compounds