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Conversion of C≡C to CO in alkynyl-metal complexes: oxidation of carbon chains capped by carbon-tricobalt clusters

Abstract
Treatment of Co₃(μ₃-CC≡CR)(μ-dppm)(CO)₇ with O₂ (air) in the presence of [FcH]PF₆ afforded Co₃{μ₃-CC(O)R}(μ-dppm)(CO)₇ by the formal conversion –C≡C– + O–O → >C–O + C≡O. In this way, complexes with R = Ph, Fc, and W(CO)₃Cp, bis-clusters {Co₃(μ-dppm)(CO)₇}₂{μ₃:μ₃-[≡C(O)(C≡C)C≡]}, {Co₃(μ-dppm)(CO)₇}₂{μ₃:μ₃-[≡C(O)(C≡C)xC(O)C≡]} (x = 1, 2), and {Co₃(μ-dppm)(CO)₇}₂{μ₃:μ₃-[≡CC(O)C≡CC₆H4C≡CC(O)C≡]}, and heterometallic bis-clusters {Co₃(μ-dppm)(CO)₇}{μ₃:μ₃-[≡CC(O)C≡CC≡]}{M₃(μ-H)₃(CO)₉} (M = Ru, Os) have been prepared. Single-crystal XRD structure determinations of several products are reported together with that of precursor {Co₃(μ-dppm)(CO)₇}₂{μ₃:μ₃-[≡C(C≡C)₂C₆H₄(C≡C)₂C≡]}.
Type
Journal Article
Type of thesis
Series
Citation
Bruce, M.I., Humphrey, P.A., Zaitseva, N.N., Nicholson, B.K., Skelton, B.W. & White, A.H. (2010). Conversion of C≡C to CO in alkynyl-metal complexes: oxidation of carbon chains capped by carbon-tricobalt clusters. Dalton Transactions, 39(37), 8801-8811.
Date
2010
Publisher
The Royal Society of Chemistry
Degree
Supervisors
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