The reaction of trimethylsilyl-substituted alkynes with 0.5 equivalents of Cp₂ZrCl₂ and 1 equivalent of Et₃Al in toluene at room temperature for 18 hours gives, after hydrolysis/deuterolysis or iodination, functionalized products of the homo-coupling of silyl-substituted alkynes in good yield. Trimethylsilyl-substituted α,ω-diynes react with the Cp₂ZrCl₂ – Et₃Al reagent system to give (1Z,2Z)-1,2-bis(iodo(trimethylsilyl)methylene)cycloalkanes after iodinolysis.