AbstractThe reactions of the metallocene generators Cp′2M(L)(η2‐Me3SiC≡CSiMe3) [1a‐Ti: Cp′ = Cp = η5‐cyclopentadienyl, M = Ti, L = none; 1b‐Ti: Cp′ = Cp* = η5‐pentamethylcyclopentadienyl, M = Ti, L = none; 1c‐Ti: Cp′2 = rac‐(ebthi) = rac‐ethylenebistetrahydroindenyl, M = Ti, L = none; 1a‐Zr: Cp′ = Cp, M = Zr, L = pyridine; 1b‐Zr: Cp′ = Cp*, M = Zr, L = none; 1c‐Zr: Cp′2 = rac‐(ebthi), M = Zr, L = none] with 1,2‐bis(4′,4′,5′,5′‐tetramethyl[1′,3′,2′]dioxaborolan‐2′‐yl)acetylene (bPinBA, 2) as a di‐heteroatom‐substituted alkyne were investigated. A slightly special reaction of 1a‐Ti with 2 produced no titanacyclopropene or titanacyclopentadiene, but instead complex 3 was produced by the coupling of two alkyne units with one of the Cp ligands to form a six‐membered ring annelated to a five‐membered one. The titanocene complexes 1b‐Ti and 1c‐Ti reacted with 2 to form the titanacylopropenes 4 and 5. The complex 1a‐Zr reacts with 2 to the corresponding zirconacyclopropene 6 as a byproduct, in which the pyridine ligand remains coordinated. If the pyridine ligand dissociates, a coupling with a second alkyne yields the zirconacyclopentadiene 7 as the main product. The reaction of the sterically more demanding zirconocene precursor 1c‐Zr also yielded the zirconacyclopentadiene 8, whereas 1b‐Zr did not react with 2. The complex rac‐(ebthi)Ti(η2‐bPinBA) (5) reacts with gaseous dry CO2 directly to form the titanafuranone 9. The molecular structures of complexes 5 and 6 were characterised by single‐crystal X‐ray crystallography.