Regio- and Stereochemical Control in Ocimene Polymerization by Half-Sandwich Rare-Earth Metal Dialkyl Complexes

The polymerization of ocimene has been first achieved by half-sandwich rare-earth metal dialkyl complexes in combination with activator and AliBu3. The regio- and stereoselectivity in the ocimene polymerization can be controlled by tuning the cyclopentadienyl ligand and the central metal of the complex. The chiral cyclopentadienyl-ligated Sc complex 1 prepares syndiotactic cis-1,4-polyocimene (cis-1,4-selectivity up to 100%, rrrr = 100%), while the corresponding Lu, Y, and Dy complexes 2–4 and the achiral pentamethylcyclopentadienyl Sc, Lu, and Y complexes 5–7 afford isotactic trans-1,2-polyocimenes (trans-1,2-selectivity up to 100%, mm = 100%).