The carbon-carbon bond formation reactions of diynes with EtMgBr can be catalyzed by Cp(2)ZrCl(2). The final products, magnesiated enynes, readily undergo stereoisomerization to give a mixture of (E) and (Z) isomers. The stoichiometric reaction of diynes with ethylene zirconocene gives zirconacyclopentenes with alkynyl substituents in the alpha position with high regioselectivities.