文摘
Treatment of rare earth metal trialkyl complexes Ln(CH2SiMe3)3(THF)2 (Ln = Sc, Lu, and Y) with 1 equiv of 伪-diimine ligands 2,6-R2C6H3N鈺怌H鈭扖H鈺怤C6H3R2-2,6 (R = iPr, Me) affords straightforwardly monoanionic iminoamido rare earth metal dialkyl complexes [2,6-R2C6H3N鈭扖H2鈭扖(CH2SiMe3)鈺怤C6H3R2-2,6]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鈭?5% 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 homopolyisoprene materials with different microstructures and compositions. The sterically crowded complexes 1鈭?b>3 give a mixture of 3,4- and trans-1,4-polyisoprenes (3,4-selectivities: 48鈭?2%, trans-1,4-selectivities: 50鈭?7%), whereas the less sterically demanding complexes 4鈭?b>6 show high 3,4-selectivities (3,4-selectivities: 90鈭?00%). In the presence of 2 equiv of AliBu3, the complexes 1鈭?b>6/activator systems exhibit higher activities and 3,4-selectivities in the living polymerization of isoprene. A similar structure鈭抮eactivity relationship in polymerization catalysis can be also observed in these ternary systems. A possible mechanism of the isoprene polymerization processes is proposed on the basis of the DFT calculations.