Living 3,4-Polymerization of Isoprene by Cationic Rare Earth Metal Alkyl Complexes Bearing Iminoamido Ligands

Treatment of rare earth metal trialkyl complexes Ln(CH2SiMe3)3(THF)2 (Ln = Sc, Lu, and Y) with 1 equiv of α-diimine ligands 2,6-R2C6H3N═CH−CH═NC6H3R2-2,6 (R = iPr, Me) affords straightforwardly monoanionic iminoamido rare earth metal dialkyl complexes [2,6-R2C6H3N−CH2−C(CH2SiMe3)═NC6H3R2-2,6]Ln(CH2SiMe3)2(THF) (1: Ln = Sc, R = iPr; 2: Ln = Lu, R = iPr; 3: Ln = Y, R = iPr; 4: Ln = Sc, R = Me; 5: Ln = Lu, R = Me; 6: Ln = Y, R = Me) in 65−85% isolated yields. X-ray analyses show these complexes have decreasing steric hindrance in the coordination spheres of the metal centers in the order 1 > 2 > 3 > 4 > 5 > 6. A mechanism involving intramolecular alkyl and hydrogen migration is supported on the basis of DFT calculations to account for ligand alkylation. Activated by [Ph3C][B(C6F5)4], all of these iminoamido rare earth metal dialkyl complexes are active for living polymerization of isoprene, with activity and selectivity being significantly dependent on the steric hindrance around the metal center to yield ho...