Chiral and achiral phosphine derivatives of alkylidyne tricobalt carbonyl clusters as catalyst precursors for (asymmetric) inter- and intramolecular Pauson-Khand reactions.

Phosphine derivatives of alkylidyne tricobalt carbonyl clusters have been tested as catalysts/catalyst precursors in intermolecular and (asymmetric) intramolecular Pauson-Khand reactions. A number of new phosphine derivatives of the tricobalt alkylidyne clusters [Co(3)(mu(3)-CR)(CO)(9)] (R = H, CO(2)Et) were prepared and characterised. The clusters [Co(3)(mu(3)-CR)(CO)(9-x)(PR'(3))(x)] (PR'(3) = achiral or chiral monodentate phosphine, x = 1-3) and [Co(3)(mu(3)-CR)(CO)(7)(P-P)] (P-P = chiral diphosphine; 1,1'- and 1,2-structural isomers) were assayed as catalysts for intermolecular and (asymmetric) intramolecular Pauson-Khand reactions. The phosphine-substituted tricobalt clusters proved to be viable catalysts/catalyst precursors that gave moderate to very good product yields (up to approximately 90%), but the enantiomeric excesses were too low for the clusters to be of practical use in the asymmetric reactions.