Metalocyclopentadiene complexes of iridium (III) and rhodium(III) have been prepared from acetylenes. Provisional structures have been assigned to these metalocycles on the basis of infrared and nmr spectra of five- and six-coordinate complexes. Cyclotrimerization of disubstituted acetylenes is catalyzed by the coordinatively unsaturated metalocycles. Using an isotopically labeled substrate, the sequential cyclotrimerization of acetylenes has been elucidated. A tentative mechanism is proposed for acetylene cyclization. © 1968, American Chemical Society. All rights reserved.