Matches in SemOpenAlex for { <https://semopenalex.org/work/W2317106066> ?p ?o ?g. }
- W2317106066 endingPage "170" @default.
- W2317106066 startingPage "160" @default.
- W2317106066 abstract "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 homopolyisoprene materials with different microstructures and compositions. The sterically crowded complexes 1−3 give a mixture of 3,4- and trans-1,4-polyisoprenes (3,4-selectivities: 48−82%, trans-1,4-selectivities: 50−17%), whereas the less sterically demanding complexes 4−6 show high 3,4-selectivities (3,4-selectivities: 90−100%). In the presence of 2 equiv of AliBu3, the complexes 1−6/activator systems exhibit higher activities and 3,4-selectivities in the living polymerization of isoprene. A similar structure−reactivity 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." @default.
- W2317106066 created "2016-06-24" @default.
- W2317106066 creator A5011196991 @default.
- W2317106066 creator A5014014197 @default.
- W2317106066 creator A5023308362 @default.
- W2317106066 creator A5027960395 @default.
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- W2317106066 creator A5070659566 @default.
- W2317106066 creator A5071890915 @default.
- W2317106066 creator A5074160086 @default.
- W2317106066 date "2010-12-06" @default.
- W2317106066 modified "2023-09-27" @default.
- W2317106066 title "Living 3,4-Polymerization of Isoprene by Cationic Rare Earth Metal Alkyl Complexes Bearing Iminoamido Ligands" @default.
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