[Sc(III)(Me)(κ2-(2,6-(i-Pr)2C6H3)NC(t-butyl)CHC(t-butyl)N(2,6-(i-Pr)2C6H3))][MeB(C6F5)3] | 412344-08-2

• 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)(Me)(κ2-(2,6-(i-Pr)2C6H3)NC(t-butyl)CHC(t-butyl)N(2,6-(i-Pr)2C6H3))][MeB(C6F5)3]
• CAS: 412344-08-2
• 化学式: C₁₉H₃BF₁₅*C₃₆H₅₆N₂Sc
• 分子量: 1088.83
• InChiKey: CQWOBCIAGRONRN-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

• 作为产物：
  描述：

  ((2,6-iPr2-C6H3)NC(tBu)CHC(tBu)N(2,6-iPr2-C6H3))Sc(methyl)2 、 三(五氟苯基)硼烷 生成 [Sc(III)(Me)(κ2-(2,6-(i-Pr)2C6H3)NC(t-butyl)CHC(t-butyl)N(2,6-(i-Pr)2C6H3))][MeB(C6F5)3]
  参考文献：
  名称：

  由 β-Diketiminato（“Nacnac”）配体框架支持的阳离子甲基钪配合物

  摘要：

  由庞大的 β-二酮亚基配体 ArNC((t)Bu)CHC((t)Bu)NAr (Ar = 2,6-(i)Pr(2)C(6)H() 支撑的无碱二甲基钪络合物3), 1) 与各种等价的强有机金属路易斯酸 B(C(6)F(5))(3) 反应生成烷基钪阳离子。使用 0.5 当量，通过光谱观察到单阳离子 μ-甲基二聚体 (2)。与另外 0.5 当量的硼烷反应得到单体甲基阳离子 3，其已被完全表征，包括通过 X 射线晶体学。该化合物通过“配体翻转”机制在 NMR 时间尺度上具有流动性。与另一个等价的硼烷反应得到独特的二号离子 4，它在 NMR 时间尺度上显示出静态结构。二甲基化合物1是硼烷或MAO型活化下乙烯聚合的高活性催化剂前体。

  DOI：

  10.1021/ja017128g

文献信息

• 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.