| 473595-02-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 473595-02-7
• 化学式: C₃₅H₅₅O₂ScSi₃
• 分子量: 637.033
• InChiKey: NDVQWOIAGKEKJN-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：

  、 双(2-((R)-4-苯基-4,5-二氢噁唑-2-基)苯基)胺 以 四氢呋喃 为溶剂， 反应 1.0h， 以74%的产率得到
  参考文献：
  名称：

  带有双（恶唑啉基苯基）酰胺配体的钪配合物：对其反应性、溶液态结构和光物理特性的分析

  摘要：

  报道了由双（恶唑啉基苯基）酰胺（R-BOPA）配体支持的钪的配位化学。R-BOPA 配体的空间要求太高，无法提供双（酰胺）配合物 [Sc(R-BOPA){N(SiMe3)2}2]，但原配体与 [Sc{N(SiMe3)2} 2Cl(THF)] (1) 得到混合酰氯复合物 [Sc(R-BOPA){N(SiMe3)2}Cl] (2)。研究了2中酰氨基和氯共配体的选择性反应；虽然氯化物配体可以通过复分解干净地去除，但 N(SiMe3)2 配体的质子化导致 R-BOPA 配体的竞争性质子化。复合物 [Sc(R-BOPA)(CH2SiMe2Ph)2] (5) 已经合成。每个含有 R-BOPA 的复合物都以两种异构形式存在。已经通过实验和计算研究了平衡，并且数据表明苯环的协同旋转使两种非对映异构体相互转化。发现所有的 R-BOPA 复合物都是发光的；在 TD-DFT 计算的辅助下，对光物理学的分析表明，

  DOI：

  10.1002/ejic.201600223
• 作为产物：
  描述：

  ScCl3(THF)2 、 lithium,methanidyl-dimethyl-phenylsilane 以 甲苯 为溶剂， 以75%的产率得到
  参考文献：
  名称：

  庞大的水杨醛亚胺配体支持的Scan和钇的有机金属配合物

  摘要：

  由三（烷基）前体[M（CH 2 SiMe 2 R）3（THF）2 ]（M = Sc，1-Sc R ; M = Y，1-Y R； R = CH 3，Ph）通过烷烃消除。新的前体1-M Ph具有更高的热稳定性和结晶度，是1-M Me衍生物的方便替代物。1-Sc博士在结晶学上已经表征。这些化合物与1当量的蛋白质配体反应，仅对于1-Y产生可分离的单（配体）双（烷基）衍生物。对于其他衍生物1-Sc，获得混合物。前一个反应的产物保留两个（2-Y Ph）或一个（3-Y Ph）THF配体。这两种化合物均已通过晶体学表征。在溶液中，两者均表现出两个几何异构体之间的通量交换，这通过可变温度NMR光谱表征。任一种化合物的加热溶液都会导致配体容易重新分布。三（烷基）1的反应用2当量protio配体的给五配位，无THF双（配体）单（烷基）配合物4-M - [R 。这些化合物具有很高的热稳定性，在140°C以上的温度

  DOI：

  10.1021/om020382c

文献信息

• 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。
• A monoanionic pentadentate ligand platform for scandium–pnictogen multiple bonds
  作者：Evan A. Patrick、Yan Yang、Warren E. Piers、Laurent Maron、Benjamin S. Gelfand

  DOI：10.1039/d1cc03481b

  日期：——

  A new monoanionic pentadentate ligand is designed to accommodate Sc = E bonds (E = N, P).

  设计了一种新的五齿配体，可容纳Sc = E键（E = N，P）。
• 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。
• 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.
• Metalation-Resistant β-Diketiminato Ligands for Thermally Robust Organoscandium Complexes
  作者：Alyson L. Kenward、Jennifer A. Ross、Warren E. Piers、Masood Parvez

  DOI：10.1021/om900283s

  日期：2009.7.13

  A new ligand design for the widely used beta-diketiminato framework implements a "remote steric bulk" strategy for the stabilization of low-coordinate, metalation-resistant organoscandium complexes. In comparison to standard ligands. Substantial improvements in thermal stability for neutral dialkyl and cationic alkyl organoscandium complexes are observed.