[(2,6-Me2C6H3NCH2C(CH2SiMe3)=NC6H3Me2-2,6)Y(CH2SiMe3)2(THF)] | 1237503-08-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(2,6-Me2C6H3NCH2C(CH2SiMe3)=NC6H3Me2-2,6)Y(CH2SiMe3)2(THF)]
• CAS: 1237503-08-0
• 化学式: C₃₄H₆₁N₂OSi₃Y
• 分子量: 687.034
• InChiKey: QPQQDYYDJFJLMQ-NPUNLENQSA-N

反应信息

• 作为产物：
  描述：

  bis(tetrahydrofuran)tris(trimethylsilylmethyl)yttrium(III) 、 glyoxalbis(2,6-dimethylphenylimine) 以 正己烷 、 甲苯 为溶剂， 以78%的产率得到[(2,6-Me2C6H3NCH2C(CH2SiMe3)=NC6H3Me2-2,6)Y(CH2SiMe3)2(THF)]
  参考文献：
  名称：

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

  摘要：

  Treatment of rare earth metal trialkyl complexes Ln(CH2SiMe3)(3)(THF)(2) (Ln = Sc, Lu, and Y) with 1 equiv of alpha-diimine ligands 2,6-R2C6H3N=CH-CH=NC6H3R2-2,6 (R = Pr-i, Me) affords straightforwardly monoanionic iminoamido rare earth metal dialkyl complexes [2,6-R2C6H3N-CH2-C(CH2-SiMe3)=NC6H3R2-2,6]Ln(CH2SiMe3)(2)(THF) (1: Ln = Sc, R = Pr-i; 2: Ln = Lu, R = Pr-i; 3: Ln = Y, R = Pr-i; 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 (AlBu3)-Bu-i, 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.

  DOI：

  10.1021/om100971d

文献信息

• Intramolecular Alkylation of α-Diimine Ligands Giving Amido—Imino and Diamido Scandium and Yttrium Complexes as Catalysts for Intramolecular Hydroamination/Cyclization
  作者：Hiroshi Kaneko、Hayato Tsurugi、Tarun K. Panda、Kazushi Mashima

  DOI：10.1021/om1002667

  日期：2010.8.9

  Treatment of alkyl complexes M(CH2SiM3)(3)-(THF)(2) (1a M=Sc; 1b M =Y) with alpha-dumine ligands, N, N'-bis(2,6-dimethylphenyl)-1,4-diaza-1,3-butadiene (2a) and N, N'-bis(2,6-dusopropylphenyl)-1,4-diaza-1,3-butadiene (2h), afforded the corresponding amido-imino complexes M(CH2-SiMe3)(2)(2,6-R2Ph-DAB-CH2SiMe3)(THF) (3a M = Sc, R = M = Sc, R = Me, 3b. M = Sc, R = 'Pr, 4a M = Y, R = Me, 4b. M = Y, R = 'Pr) by selective monoalkylatron of one of two C=N bonds of the ligands followed by intramolecular 11 migration, while in the reactions with a less bulky alpha-dimine ligand, N,N'-bis(4-methylphenyl)-1,4-diaza-1,3-butadiene (2c), complex la gave an diamido complex ScCH2SiMe3(4- MePh-DAB-(CH2SiMe3)(2))-(THF)(2) (5c) as a product of the double alkylation Upon heating a hexane solution of 3b, intramolecular activation of a C-H bond of an isopropyl group of the ligand proceeded to give a scandium monoalkyl complex ScH2SiMe3(CH2C2H4-6-'PrPh-2,6'Pr2Ph-DAB-DH2SiMe3)(THF) (6h). Among them, amido-imino complexes of yttrium became catalysts for intramolecular hydroamination/cylization of 2,2-dimethyl-4-pentenylamine at at room temperature