Département de chimie moléculaire

The PtCl₂-catalyzed cycloisomerization of 1,6-enynes is considerably accelerated in the presence of carbon monoxide. The effect of CO has been explained by the reinforcement of the electrophilicity of the alkyne moiety once ligated to the π-acidic [PtCl₂(CO)] fragment. However, platinum is also described as weakly capable of back-donation toward CO. A theor. study has been carried out to shed light on this apparent contradiction. An alternative explanation based on the approach of CO onto the [PtCl₂(η₄-(1,6-enyne))] complex is proposed. When CO is ligated to PtCl₂, the triple-bond coordination is favored, yet there is no pos. influence on the formation of the cyclopropylcarbene key intermediate. The role of CO is actually comparable to that of a water mol.