Regiochemistry in the Pauson-Khand reaction: Has a trans effect been overlooked?

Alkyne-dicobalt hexacarbonyl complexes have been studied by DFT to examine whether electronic differences in the acetylenic substituents could play a role in determining the regiochemical outcome in the Pauson-Khand reaction. It appears that in some instances the regiochemistry is, in fact, governed exclusively by the electronic nature of the acetylenic substituents throug h the discriminant loss of a carbon monoxide ligand.