| 473595-12-9

• 分子结构分类: 有机化合物 - 苯类化合物
• CAS: 473595-12-9
• 化学式: C₃₅H₅₅O₂Si₃Y
• 分子量: 680.983
• InChiKey: ASWVWZPGFTZUSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  2,4-di-tert-butyl-6-bis(2-(diethylamino)ethyl)aminomethylphenol 、 以 四氢呋喃 为溶剂， 以32%的产率得到[((Et2NC2H4)2NCH2C6H2-3,5-(CMe3)2-2-O)Y(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

• Monocationic Bis-Alkyl and Bis-Allyl Yttrium Complexes: Synthesis, ⁸⁹Y NMR Characterization, Ethylene or Isoprene Polymerization, and Modeling
  作者：Alexis D. Oswald、Aymane El Bouhali、Emmanuel Chefdeville、Pierre-Alain R. Breuil、Hélène Olivier-Bourbigou、Julien Thuilliez、Florent Vaultier、Aimery De Mallmann、Mostafa Taoufik、Lionel Perrin、Christophe Boisson

  DOI：10.1021/acs.organomet.0c00709

  日期：2021.1.25

  NMR, and EXAFS for the allyl cationic complex [Y[1,3-(SiMe3)2C3H3]2(THF)2][B(C6F5)4]. More specifically, a 1H-coupled 89Y INEPT sequence has been developed in order to quantify the metal/alkyl ligand stoichiometry of both synthesized neutral tris-alkyl and cationic bis-alkyl yttrium complexes. The activity of the cationic complexes toward ethylene and isoprene homopolymerization has been assessed.

  钇与各种双烷基和双烯丙基配体Y（CH 2 SiMe 2 Ph）2（THF）4 ] [B（C 6 F 5）4 ]，[Y（CH 2 C 6 H 4 NMe 2）的单阳离子络合物）2（THF）2 ] [B（C 6 F 5）4 ]和[Y [1,3-（SiMe 3）2 C 3 H 3 ] 2（THF）2 ] [B（C 6 F 5）4通过使用硼酸苯胺盐[PhNMe 2 H] [B（C 6 F 5）4 ]质子分解相应的均三烷基或-烯丙基配合物来制备[ ]。所得离子对络合物已通过不同技术进行了分离和表征，例如元素分析，1 H，13 C和89 Y NMR，以及烯丙基阳离子络合物[Y [1,3-（SiMe 3）2 C 3 H 3 ] 2（THF）2 ] [B（C 6 F 5）4 ]。更具体地说，是1为了量化合成的中性三-烷基和阳离子双-烷基钇配合物的金属/烷基配体化学计量，已经开发了H偶联的89 Y INEP
• Synthesis and thermal reactivity of organoscandium and yttrium complexes of sterically less bulky salicylaldiminato ligandsElectronic supplementary information (ESI) available: Further experimental details. See http://www.rsc.org/suppdata/dt/b3/b303097k/
  作者：David J. H. Emslie、Warren E. Piers、Masood Parvez

  DOI：10.1039/b303097k

  日期：——

  Scandium and yttrium bis(ligand) mono(alkyl) complexes, of N-phenyl (L1) N-2-isopropylphenyl (L2) and N-mesityl (L3) substituted ortho-tert-butylsalicylaldiminato ligands were prepared by alkane elimination from [M(CH2SiMe2R)3(THF)2] (R = Me, Ph) and two equivalents of proteo ligand (HL). The resulting [L2M(THF)n(CH2SiMe2R)] (n = 0–2, L = L1 (1), L2 (2), L3 (3)) complexes are thermally unstable, decomposing rapidly between −20 and 20 °C. In order to gain insight in to ligand features necessary to impart thermal stability in early transition metal organometallic chemistry, the decomposition pathways of 1–3 have been investigated and compared with more sterically congested N-2,6-diisopropylphenyl substituted analogues. Compounds 1 and 2 decompose rapidly and cleanly at room temperature by 1,3-migration of the entire CH2SiMe2R group to the aldimine carbon. By contrast, L3 mono(alkyls) 3 decompose cleanly by metallation of an ortho-C6H2Me3 group. In the case of yttrium, the metallated alkyl undergoes subsequent 1,3-migration to the aldimine carbon, forming a five-membered C4N-ring.

  通过烷烃消去法，从[M(CH2SiMe2R)3(THF)2]（R = Me，Ph）和两个当量的蛋白配体（HL）制备了 N-苯基（L1）、N-2-异丙基苯基（L2）和 N-甲烷基（L3）取代的正叔丁基水杨醛二烷基配体的钪和钇双(配体)单(烷基)配合物。生成的[L2M(THF)n(CH2SiMe2R)]（n = 0-2，L = L1 (1)、L2 (2)、L3 (3)）复合物热不稳定，在 -20 至 20 °C 之间迅速分解。为了深入了解在早期过渡金属有机金属化学中赋予热稳定性所必需的配体特征，我们研究了 1-3 复合物的分解途径，并将其与立体性更强的 N-2,6-二异丙基苯基取代类似物进行了比较。化合物 1 和 2 通过整个 CH2SiMe2R 基团向醛二胺碳的 1,3 迁移，在室温下迅速而干净地分解。相比之下，L3 单（烷基）3 通过正交-C6H2Me3 基团的金属化作用分解得很干净。在钇的情况下，金属化的烷基随后会发生 1,3 迁移到醛亚胺碳上，形成一个五元 C4N 环。
• Organo-scandium and -yttrium complexes supported by a salicylaldiminato ligand
  作者：David J. H. Emslie、Warren E. Piers、Robert MacDonald

  DOI：10.1039/b108336h

  日期：2002.1.23

  Reaction of a salicylaldiminato ligand with M(CH2SiMe2Ph)3(THF)2 (M = Sc, Y) leads to diastereoselective formation of highly thermally stable L2MR complexes whose reactivity with dihydrogen to form Group 3 metal hydrides is described.

  水杨醛配体与 M(CH2SiMe2Ph)3(THF)2（M = Sc、Y）反应，非对映选择性地形成了热稳定性极高的 L2MR 复合物，这些复合物与二氢反应生成了第 3 族金属氢化物。
• Cationic Phenoxyimine Complexes of Yttrium: Synthesis, Characterization, and Living Polymerization of Isoprene
  作者：Alexis D. Oswald、Ludmilla Verrieux、Pierre-Alain R. Breuil、Hélène Olivier-Bourbigou、Julien Thuilliez、Florent Vaultier、Mostafa Taoufik、Lionel Perrin、Christophe Boisson

  DOI：10.1021/acs.organomet.2c00238

  日期：2022.8.8

  analysis, NMR (1H, 13C, and 89Y), and more specifically by the 1H-coupled 89Y INEPT. The reactivity of the cationic complex toward isoprene polymerization was evaluated in the presence of trialkylaluminum. This catalyst enables the living cis-1,4 polymerization of isoprene selectively. The influence and the role played by alkylaluminum are discussed based on the screening of a set of aluminum reagents

  苯氧亚胺阳离子配合物[L 1 Y(CH 2 SiMe 2 Ph)(THF) 3 ][BArF] (L 1 = (3- t Bu)-(O)–C 6 H 3 –CH=N-(2, 6 - i Pr-C 6 H 3 )) 由均配的[Y(CH 2 SiMe 2 Ph) 3 (THF) 2 ] 钇络合物和苯氧基亚胺配体HL 1开始制备，随后通过苯胺硼酸盐进行阳离子化。通过元素分析、NMR ( 1 H, 13C 和89 Y)，更具体地说是1 H 耦合的89 Y INEPT。在三烷基铝存在下评估阳离子络合物对异戊二烯聚合的反应性。该催化剂能够选择性地实现异戊二烯的活性顺式-1,4 聚合。在筛选了一套铝试剂的基础上，讨论了烷基铝的影响和作用。通过在 DFT 水平上进行的计算机制研究，一种解释顺式/反式的阳离子复合物/3,4 鉴定了实验观察到的选择性。此外，由预催化混合物产生的配合物的计算机形态表明形成了稳定的