Low-valent cobalt complexes can promote intramolecular (3 + 2) cycloadditions of alkyne-tethered cyclopropenes to provide bicyclic systems containing highly substituted cyclopentadienyl moieties with electronically diverse functional groups. The adducts can be easily transformed into new types of CpRh(III) and CpIr(III) complexes, which show catalytic activity in several relevant transformations. Preliminary computational (DFT) and experimental studies provide relevant information on the mechanistic peculiarities of the cobalt-catalyzed process and allow us to rationalize its advantages over the homologous rhodium-promoted reaction.
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