Abstract
Bis(pentamethylcyclopentadienyl)metal dichlorides, CP* 2MCl 2 (M = Ti, Zr, Hf), react with vinyllithium in the molar ratio1/2to form the corresponding divinyl compounds Cp* 2M(CH=CH 2) 2. The hafnium compound can be isolated pure. The titanium and zirconium compounds can be detected by low-temperature NMR spectroscopy, but they undergo rearrangements at room temperature. Cp* 2Zr-(CH=CH 2) 2 forms an equilibrium with C p 2 ★ Z r C H = C H C H 2 ︹ C H 2 as the zirconacyclopent-2-ene derivative whereas Cp* 2Ti(CH=CH 2) 2 surprisingly is converted quantitatively into C p 2 ★ T i C ( = C H 2 ) C H 2 ︹ C H 2 which exhibits a titanacyclobutane derivative with an exocyclic methylidene group.
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