Zirconium complexes of some [5]cumulene derivatives were studied for their variable coordination modes and haptotropic shifts. Some [5]cumulene compounds reacted with zirconocene(II) species to afford 1-zirconacyclopent-3-yne complexes that have five-membered cycloalkyne structures. Only a few [5]cumulene compounds afforded η2-coordinated complexes in the presence of neutral ligands such as trimethylphosphine and tert-butyl isocyanide. Interconversion between the five-membered structure and the η2-complex was observed. Investigation of [5]cumulene derivatives of various cycloalkylidene moieties indicated that the η2-complex was preferred when the [5]cumulene has bulkier substituents. A [5]cumulene with 2,2,6,6-tetramethylcyclohexylidene groups much preferred the 1-zirconacyclopent-3-yne structure to η2-coordination. In sharp contrast, the η2-coordinated complex was favored for a [5]cumulene with 2,2,7,7-tetramethylcycloheptylidene groups in the presence of PMe3. Small differences in steric environments ca...