Iron, Cobalt and Nickel Carbide--Carbonyl Clusters by CO Scission

A new approach to the synthesis in good yields of known cobalt and iron carbide--carbonyl clusters by CO cleavage in mild conditions is reported. Cleavage of CO results from attaching an acetyl or benzoyl carbocation to the oxygen atom, and by transfer of electrons from an external source. This synt...

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Bibliographic Details
Published in:Philosophical transactions of the Royal Society of London. Series A: Mathematical and physical sciences 1982-12, Vol.308 (1501), p.47-57
Main Authors: Longoni, G., Ceriotti, A., Della Pergola, R., Manassero, M., Perego, M., Piro, G., Sansoni, M.
Format: Article
Language:English
Subjects:
Adducts
Atoms
Carbides
Carbon monoxide
Chlorides
Cobalt
Iron
Molecular clusters
Oxygen
Rock cleavage
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Summary:A new approach to the synthesis in good yields of known cobalt and iron carbide--carbonyl clusters by CO cleavage in mild conditions is reported. Cleavage of CO results from attaching an acetyl or benzoyl carbocation to the oxygen atom, and by transfer of electrons from an external source. This synthetic approach to carbide molecular clusters may be of some significance with respect to the formation of carbide atoms on to metal crystallites. Attempts to synthesize nickel carbide clusters with the same approach have only been partly successful. The new [Ni$_{9}$C(CO)$_{17}$]$^{2-}$ and [Ni$_{8}$C(CO)$_{16}$]$^{2-}$ have been obtained more conveniently from the reaction of [Ni$_{6}$(CO)$_{12}$]$^{2-}$ with CCl$_{4}$. The related reaction of [Ni$_{6}$(CO)$_{12}$]$^{2-}$ with Co$_{3}$(CO)$_{9}$CCl results in the formation of the mixed-metal carbide cluster [Co$_{3}$Ni$_{9}$C(CO)$_{20}$]$^{3-}$. This compound is degraded under a carbon monoxide and hydrogen mixture (25 degrees C, 1 atm) to Ni(CO)$_{4}$, [Co(CO)$_{4}$]$^{-}$ and ethane. Intermediate formation of [Co$_{3}$Ni$_{7}$(C-C)(CO)$_{15}$]$^{3-}$, in which the two carbide atoms show an interatomic separation of 1.43 angstrom, or of a related species, would provide a possible pathway for C-C bond formation.
ISSN:1364-503X
0080-4614
1471-2962
2054-0272
DOI:10.1098/rsta.1982.0145