[Sc(III)(CH2SiMe3)2(κ2-(2,6-(i-Pr)2C6H3)NC(t-butyl)CHC(t-butyl)N(2,6-(i-Pr)2C6H3))] | 327596-43-0

• 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: [Sc(III)(CH2SiMe3)2(κ2-(2,6-(i-Pr)2C6H3)NC(t-butyl)CHC(t-butyl)N(2,6-(i-Pr)2C6H3))]
• CAS: 327596-43-0
• 化学式: C₄₃H₇₅N₂ScSi₂
• 分子量: 721.209
• InChiKey: JUAGYIYIMQLLAW-HHHMVCBXSA-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：

  [Sc(III)(CH2SiMe3)2(κ2-(2,6-(i-Pr)2C6H3)NC(t-butyl)CHC(t-butyl)N(2,6-(i-Pr)2C6H3))] 以 甲苯 为溶剂， 以24%的产率得到
  参考文献：
  名称：

  Dialkylscandium Complexes Supported by β-Diketiminato Ligands:  Synthesis, Characterization, and Thermal Stability of a New Family of Organoscandium Complexes

  摘要：

  Several diorganoscandium complexes stabilized by the beta -diketiminato ligands (Ar)NC(R)CHC(R)N(Ar) (Ar = 2,6-iPr-C6H3; R = CH3 (ligand a), R = rBu (ligand b)) have been synthesized. Reaction of the lithium salts of the ligands with ScCl3. 3THF leads to the complexes LScCl2(THF)(n), which may be readily alkylated to form the dialkyl derivatives. Most are isolated as base-free, four-coordinate complexes. Several have been characterized via X-ray crystallography, and a detailed discussion of their structures is presented. Steric interactions between Ar and the Sc-alkyl groups force the scandium to adopt an out-of-plane bonding mode. In solution, this is manifested via a fluxional process which equilibrates the two diastereotopic alkyl groups and ligand groups as well. The barriers to this process roughly correlate with the steric bulk of the alkyl substituents. At elevated temperatures, the dialkyl derivatives LScR2 undergo a metalation process whereby one of the alkyl groups is eliminated as RH, and a ligand iPr group is metalated in the methyl position. These reactions are first order in scandium complex, and activation parameters of DeltaH(double dagger) = 19.7(6) kcal mol(-1) and DeltaS(double dagger) = -17(2) cal mol(-1) K-1 were measured for the loss of Me4Si from (Ligb)Sc(CH2SiMe3)(2).

  DOI：

  10.1021/om010131o
• 作为产物：
  描述：

  以 甲苯 为溶剂， 生成 [Sc(III)(CH2SiMe3)2(κ2-(2,6-(i-Pr)2C6H3)NC(t-butyl)CHC(t-butyl)N(2,6-(i-Pr)2C6H3))]
  参考文献：
  名称：

  Dialkylscandium Complexes Supported by β-Diketiminato Ligands:  Synthesis, Characterization, and Thermal Stability of a New Family of Organoscandium Complexes

  摘要：

  Several diorganoscandium complexes stabilized by the beta -diketiminato ligands (Ar)NC(R)CHC(R)N(Ar) (Ar = 2,6-iPr-C6H3; R = CH3 (ligand a), R = rBu (ligand b)) have been synthesized. Reaction of the lithium salts of the ligands with ScCl3. 3THF leads to the complexes LScCl2(THF)(n), which may be readily alkylated to form the dialkyl derivatives. Most are isolated as base-free, four-coordinate complexes. Several have been characterized via X-ray crystallography, and a detailed discussion of their structures is presented. Steric interactions between Ar and the Sc-alkyl groups force the scandium to adopt an out-of-plane bonding mode. In solution, this is manifested via a fluxional process which equilibrates the two diastereotopic alkyl groups and ligand groups as well. The barriers to this process roughly correlate with the steric bulk of the alkyl substituents. At elevated temperatures, the dialkyl derivatives LScR2 undergo a metalation process whereby one of the alkyl groups is eliminated as RH, and a ligand iPr group is metalated in the methyl position. These reactions are first order in scandium complex, and activation parameters of DeltaH(double dagger) = 19.7(6) kcal mol(-1) and DeltaS(double dagger) = -17(2) cal mol(-1) K-1 were measured for the loss of Me4Si from (Ligb)Sc(CH2SiMe3)(2).

  DOI：

  10.1021/om010131o

文献信息

• Synthesis, Structure, and Ion Pair Dynamics of β-Diketiminato-Supported Organoscandium Contact Ion Pairs
  作者：Paul G. Hayes、Warren E. Piers、Masood Parvez

  DOI：10.1021/om050007v

  日期：2005.3.1

  (Ar)NC(R)CHC(R)N(Ar) (Ar = 2,6-iPr-C6H3; R = CH3 (LMe), R = tBu (LtBu)) has been prepared by reaction of LScR2 with perfluorinated boranes B(C6F5)3 and (C12F8)B(C6F5). While the LMe ancillary lacked sufficient steric bulk to prevent C6F5 transfer to the metal center, the LtBu derivatives were quite robust in solution. Although these species were subject to thermal decomposition via metalation of an

  由β-二酮亚胺基配体（Ar）NC（R）CHC（R）N（Ar）（Ar = 2,6- iPr-C 6 H 3；R = CH 3（L Me），R = t卜（L吨通过LScR 2与全氟化硼烷B（C 6 F 5）3和（C 12 F 8）B（C 6 F 5）反应制备了Bu））。虽然L Me辅助物缺乏足够的空间体积以防止C 6 F 5转移到金属中心，但L tBu衍生物在溶液中非常稳定。虽然这些物种是通过异丙基和RH的损失的金属化受到热分解（Δ小号⧧ = -7.0（7）欧盟和Δ Η ⧧ = 21.5（2）千卡摩尔- 1），该处理是不足够快速阻碍了其丰富的有机金属化学的发展。对溶液和固态结构进行了详细研究，揭示了exo-和内-MeB（Ar F）3的存在如果烷基金属很小，则为异构体。详细的NMR研究（低温EXSY）可以观察分子间和分子内离子对的重组过程，其机理根据“溶剂分离的离子对”的参与进行了讨论。这是第一
• Reactivity of Scandium β-Diketiminate Alkyl Complexes with Carbon Dioxide
  作者：Francis A. LeBlanc、Andreas Berkefeld、Warren E. Piers、Masood Parvez

  DOI：10.1021/om2012002

  日期：2012.2.13

  The reactions of two highly air- and moisture-sensitive scandium bis(alkyls) supported by a bulky beta-diketiminato (nacnac) ligand with carbon dioxide are described. [kappa(2)-ArNC(Bu-t)CHC(Bu-t)NAr]ScR2 (Ar = 2,6-(Pr2C6H3)-Pr-t; R = CH3, 1a; R = CH2SiMe3, 1b) react rapidly with CO2 to give mixtures of mono- and bis(carboxylato) insertion products 2a/2b and 3a/3b depending on the stoichiometry and conditions of the reaction. Compound 2a (R = CH3) is a dimeric complex with bridging acetato groups, as determined by X-ray crystallography. These compounds were characterized by NMR spectroscopy, and 3a could be isolated in pure form. Treatment of these compounds with excess CO2 resulted in addition to the central carbon of the Sc(nacnac) six-membered ring and displacement of the nitrogen donors to yield dimeric scandium carboxylates 4a/4b; compound 4b was characterized by X-ray crystallography. Reactions of the nacnac scandium cations formed upon abstraction of one or two methides from la using B(C6F5)(3) with CO2 were also explored. Although the products were qualitatively more thermally robust, eventually ligand displacement occurred in these cationic acetato complexes as well. Nevertheless, insertion products were characterizable in solution using NMR spectroscopy. Overall, this study shows the facility with which CO2 is taken up by scandium alkyls but that the nacnac ligand framework is too reactive to support chemistry aimed at catalytic conversion of CO2 into other products.