Tungsten hexacarbonyl

Preparation, properties, and structure

Like many metal carbonyls, W(CO)6 is generally prepared by "reductive carbonylation", which involves the 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".Another means of preparation involves heating iron pentacarbonyl and WCl6, resulting in the formation of ferrous chloride. The compound is relatively air-stable. It is sparingly soluble in nonpolar organic solvents. Tungsten carbonyl is widely used in electron beam-induced deposition technique - it is easily vaporized and decomposed by the electron beam providing a convenient source of tungsten atoms.

W(CO)6 adopts an octahedral geometry consisting of six rod-like CO ligands radiating from the central W atom with dipole moment 0 debye.

Reactivity

All reactions of W(CO)6 commence with displacement of some CO ligands in W(CO)6. W(CO)6 behaves similarly to the Mo(CO)6 but tends to form compounds that are kinetically more robust. thumb|left|144px|[[Cyclopentadienyltungsten tricarbonyl dimer]] ((C5H5)2W2(CO)6) is produced from W(CO)6.

Treatment of tungsten hexacarbonyl with sodium cyclopentadienide followed by oxidation of the resulting NaW(CO)3(C5H5) gives cyclopentadienyltungsten tricarbonyl dimer.

One derivative is the dihydrogen complex W(CO)3[P(C6H11)3]2(H2).

Three of these CO ligands can be displaced by acetonitrile. W(CO)6 has been used to desulfurize organosulfur compounds and as a precursor to catalysts for alkene metathesis.

Safety and handling

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

References

References

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4. (2018). "Inorganic Chemistry". Pearson Education, Limited.
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