[((Me3CSC2H4)2NCH2C6H2-3,5-(CMe3)2-2-O)Sc(CH2SiMe2Ph)2] | 931833-81-7

• 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: [((Me3CSC2H4)2NCH2C6H2-3,5-(CMe3)2-2-O)Sc(CH2SiMe2Ph)2]
• 英文别名: 2-[[Bis(2-tert-butylsulfanylethyl)amino]methyl]-4,6-ditert-butylphenolate;methanidyl-dimethyl-phenylsilane;scandium(3+)
• CAS: 931833-81-7
• 化学式: C₄₅H₇₄NOS₂ScSi₂
• 分子量: 810.348
• InChiKey: JDQQFQSEEJJDQS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  11.17
• 重原子数：
  52
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  76.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  、 (Me3CSC2H4)2NCH2C6H2-3,5-(CMe3)2-2-OH 以 四氢呋喃 为溶剂， 以16%的产率得到[((Me3CSC2H4)2NCH2C6H2-3,5-(CMe3)2-2-O)Sc(CH2SiMe2Ph)2]
  参考文献：
  名称：

  具有四齿状（L，L，N，O； L = N，O，S）单阴离子配体的第3组二烷基配合物：合成和反应性

  摘要：

  Tripodal, tetradentate phenols, (LCH2)(2)NCH2-C6H2-3,5-(CMe3)(2)-2-OH (L = CH2OCH3 (1), CH2NEt2 (2), 2-C5H4N (3), CH2SCMe3 (5), CH2NMe2 (6)), were synthesized, and metalations were performed via alkane elimination from yttrium and scandium trialkyl complexes to generate the corresponding dialkyl complexes [(LCH2CH2)(2)NCH2-C6H2-3,5-(CMe3)(2)-2-O]MR2 (M = Y, L = OCH3, R = CH2SiMe2Ph (7a); M = Y, L = NEt2, R = CH2SiMe2Ph (7b); M = Sc, L = OCH3, R = CH2SiMe2Ph (8a); M = Sc, L = SCMe3, R = CH2SiMe2Ph (8b); M = Y, L = OCH3, R = CH2SiMe3 (9); M = Sc, L = OCH3, R = CH2SiMe3 (10)). X-ray crystallographic studies show that 7a,b and 8a adopt, in the solid state, mononuclear structures of C-1 symmetry. The H-1 NMR spectra of these dialkyl complexes in benzene-d(6) at high temperatures reveal exchange processes involving the ether groups and the alkyl groups. The dynamic behavior of species 7a, 8a, and 10 in toluene-d(8) was investigated by variable-temperature H-1 NMR spectroscopy. The activation parameters of the fluxional processes for 7a, 8a, and 10 were determined by line-shape and Eyring analyses (for 7a, Delta H = 7.3 +/- 0.3 kcal/mol and Delta S = -16 +/- 1.4 cal/(mol K); for 8a, Delta H = 9.9 +/- 0.5 kcal/mol and Delta S = -15.3 +/- 1.8 cal/ (mol K); for 10, Delta H = 10.8 +/- 0.6 kcal/mol and Delta S = -11.4 +/- 1.9 cal/(mol K)). These data establish that the dialkyl complexes 7a, 8a, and 10 undergo a nondissociative exchange process. The scandium dialkyl complex [(C5H4N-2-CH2)(2)NCH2-C6H2-3,5-(CMe3)(2)-2-O]Sc(CH2SiMe2Ph)(2) (11) was found to undergo clean activation of a C-H bond of a methylene linking a pyridine to the central nitrogen donor. This process follows first-order kinetics (k = [2.8(3)] x 10(-4) s(-1) at 0 degrees C). The yttrium dialkyl complexes 7a and 9 react with 1 equiv of [PhNHMe2](+)[B(C6F5)(4)](-) in chlorobenzene-d(5), to generate a solution that slowly polymerizes ethylene. Compounds 7-10 also polymerize ethylene with low activity upon activation with MAO.

  DOI：

  10.1021/om0608612

文献信息

• Group 3 Dialkyl Complexes with Tetradentate (L, L, N, O; L = N, O, S) Monoanionic Ligands:  Synthesis and Reactivity
  作者：Smaranda C. Marinescu、Theodor Agapie、Michael W. Day、John E. Bercaw

  DOI：10.1021/om0608612

  日期：2007.2.1

  Tripodal, tetradentate phenols, (LCH2)(2)NCH2-C6H2-3,5-(CMe3)(2)-2-OH (L = CH2OCH3 (1), CH2NEt2 (2), 2-C5H4N (3), CH2SCMe3 (5), CH2NMe2 (6)), were synthesized, and metalations were performed via alkane elimination from yttrium and scandium trialkyl complexes to generate the corresponding dialkyl complexes [(LCH2CH2)(2)NCH2-C6H2-3,5-(CMe3)(2)-2-O]MR2 (M = Y, L = OCH3, R = CH2SiMe2Ph (7a); M = Y, L = NEt2, R = CH2SiMe2Ph (7b); M = Sc, L = OCH3, R = CH2SiMe2Ph (8a); M = Sc, L = SCMe3, R = CH2SiMe2Ph (8b); M = Y, L = OCH3, R = CH2SiMe3 (9); M = Sc, L = OCH3, R = CH2SiMe3 (10)). X-ray crystallographic studies show that 7a,b and 8a adopt, in the solid state, mononuclear structures of C-1 symmetry. The H-1 NMR spectra of these dialkyl complexes in benzene-d(6) at high temperatures reveal exchange processes involving the ether groups and the alkyl groups. The dynamic behavior of species 7a, 8a, and 10 in toluene-d(8) was investigated by variable-temperature H-1 NMR spectroscopy. The activation parameters of the fluxional processes for 7a, 8a, and 10 were determined by line-shape and Eyring analyses (for 7a, Delta H = 7.3 +/- 0.3 kcal/mol and Delta S = -16 +/- 1.4 cal/(mol K); for 8a, Delta H = 9.9 +/- 0.5 kcal/mol and Delta S = -15.3 +/- 1.8 cal/ (mol K); for 10, Delta H = 10.8 +/- 0.6 kcal/mol and Delta S = -11.4 +/- 1.9 cal/(mol K)). These data establish that the dialkyl complexes 7a, 8a, and 10 undergo a nondissociative exchange process. The scandium dialkyl complex [(C5H4N-2-CH2)(2)NCH2-C6H2-3,5-(CMe3)(2)-2-O]Sc(CH2SiMe2Ph)(2) (11) was found to undergo clean activation of a C-H bond of a methylene linking a pyridine to the central nitrogen donor. This process follows first-order kinetics (k = [2.8(3)] x 10(-4) s(-1) at 0 degrees C). The yttrium dialkyl complexes 7a and 9 react with 1 equiv of [PhNHMe2](+)[B(C6F5)(4)](-) in chlorobenzene-d(5), to generate a solution that slowly polymerizes ethylene. Compounds 7-10 also polymerize ethylene with low activity upon activation with MAO.