[(1,1'-ferrocenylene(NSi(tBu)Me2)2)Sc(tetrahydrofuran)(CH2C6H3Me2-3,5)] | 1007235-67-7

• 英文名称: [(1,1'-ferrocenylene(NSi(tBu)Me2)2)Sc(tetrahydrofuran)(CH2C6H3Me2-3,5)]
• 英文别名: (1,1'-ferrocenylene(NSitBuMe2)2)Sc(CH2-3,5-Me2C6H3)(THF)；[(1,1'-fc(NSi(tBu)Me2)2)Sc(THF)(CH2C6H3Me2-3,5)]；(1,1'-fc(NSi(t)BuMe2)2)Sc(CH2-3,5-Me2C6H3)(THF)；(scandium)(THF)(CH2Xy-3,5)(fc(NSitBuMe2)2)；Sc(fc[NSi(t)BuMe2]2)(CH2Xy-3,5)(THF)
• CAS: 1007235-67-7
• 化学式: C₃₅H₅₇FeN₂OScSi₂
• 分子量: 678.824
• InChiKey: BBDTZEGHOVEJOV-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：

  [(1,1'-ferrocenylene(NSi(tBu)Me2)2)Sc(tetrahydrofuran)(CH2C6H3Me2-3,5)] 、 碘甲烷 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  二茂铁二酰胺配体支持的钪芳烃倒夹心配合物

  摘要：

  报道了第一个由二茂铁二酰胺配体 (NN(fc)) 支持的钪芳烃倒夹心配合物的合成和表征。通过使用 (NN(fc))ScI(THF)(2) 作为前体和钾石墨 (KC(8)) 作为还原剂，萘和蒽配合物 [(NN(fc))Sc](2 )(μ-C(10)H(8)) 和 [(NN(fc))Sc](2)(μ-C(14)H(10)) 分别以中等至高产率合成和分离. 两种分子结构都具有倒夹心几何形状，并表现出较短的 Fe-Sc 距离。使用 DFT 计算来了解这些新的钪芳烃配合物的电子结构。[(NN(fc))Sc](2)(μ-C(14)H(10)) 的变温 NMR 光谱研究表明在溶液中可以使用两种不同的结构。反应性研究表明，萘配合物 [(NN(fc))Sc](2)(μ-C(10)H(8)) 可以转化为相应的蒽类 [(NN(fc))Sc](2 )(μ-C(14)H(10)) 和 [(NN(fc))Sc](2)(μ-C(10)H(8))

  DOI：

  10.1021/ja204304f
• 作为产物：
  描述：

  ((1,1′-ferrocenediyl)(NSitBuMe2)2) 、 Sc(CH₂C₆H₃(CH₃)₂-3,5)₃(tetrahydrofuran)₃ 以 甲苯 为溶剂， 以80%的产率得到[(1,1'-ferrocenylene(NSi(tBu)Me2)2)Sc(tetrahydrofuran)(CH2C6H3Me2-3,5)]
  参考文献：
  名称：

  Scandium Alkyl Complexes Supported by a Ferrocene Diamide Ligand

  摘要：

  Synthesis of a scandium dimethylbenzyl complex supported by a ferrocene diamide ligand was accomplished by alkane elimination from Sc(CH(2)Xy-3,5)(3)(THF)(2). The scandium dimethylbenzyl complex Sc(fc[NSi(tBu)Me-2](2))(CH(2)Xy-3,5)(THF), 2-(CH(2)Xy-3,5)(THF), was used as a starting material for the synthesis of the corresponding chloride-bridged dimer, (2-CI)(2), which, in turn, led to a scandium bis(neo-pentyl) ate salt, Li[2Np(2)]. Attempts to remove the coordinated THF molecule from 2-(CH(2)Xy-3,5)(THF) with AlMe3 led to the isolation of a scandium methyl complex with two coordinated AlMe3 molecules, 2-Me(AlMe3)(2). Compound 2-Me(AlMe3)(2) led to a scandium methyl complex, 2-Me(THF)(2), by stirring in THF. All ferrocene diamido compounds were characterized by X-ray crystallography. DFT calculations on model compounds were used to explain the stability of the compounds synthesized and to probe the existence of an iron-scandium interaction. Compounds 2-(CH(2)Xy-3,5)(THF) and 2-Me(AlMe3)(2) polymerize L-lactide.

  DOI：

  10.1021/om7007277

文献信息

• Reactions of Group III Biheterocyclic Complexes
  作者：Colin T. Carver、Diego Benitez、Kevin L. Miller、Bryan N. Williams、Ekaterina Tkatchouk、William A. Goddard、Paula L. Diaconescu

  DOI：10.1021/ja902794w

  日期：2009.7.29

  Group III alkyl complexes supported by a ferrocene diamide ligand (1,1'-fc(NSi(t)BuMe(2))(2)) have been found to be reactive toward aromatic N-heterocycles such as 1-methylimidazole and pyridines. These reactions were investigated experimentally and computationally. An initial C-H activation event is followed by a coupling reaction to form biheterocyclic complexes, in which one of the rings is dearomatized

  已发现由二茂铁二酰胺配体 (1,1'-fc(NSi(t)BuMe(2))(2)) 支持的第 III 组烷基配合物对芳香族 N-杂环（如 1-甲基咪唑和吡啶）具有反应性。通过实验和计算研究了这些反应。最初的 CH 活化事件之后是偶联反应以形成双杂环复合物，其中一个环被脱芳构化。在1-甲基咪唑的情况下，双杂环化合物不能被分离并进一步导致咪唑开环产物；在吡啶的情况下，它转化为具有双键扩展共轭的异构体。根据实验和计算结果提出了两种反应的机理。
• Insertion reactions of scandium pyridyl complexes supported by a ferrocene diamide ligand
  作者：Colin T. Carver、Paula L. Diaconescu

  DOI：10.1016/j.jallcom.2008.10.007

  日期：2009.12

  C)-pyridyl complexes, scandium η2(N,C)-pyridyl complexes supported by a ferrocene diamide ligand react further with pyridines to give coupling products. Although most of their insertion reactions with unsaturated substrates are similar to those of previous yttrocene and zirconocene complexes, in the reaction with butadiene, higher reactivity than the one reported for the yttrocene complex was observed

  摘要与早期过渡金属 η2(N,C)-吡啶基配合物的报道实例不同，由二茂二酰胺配体支持的钪 η2(N,C)-吡啶基配合物与吡啶进一步反应生成偶联产物。尽管它们与不饱和底物的大多数插入反应与之前的茂金属和二茂锆配合物的插入反应相似，但在与丁二烯的反应中，观察到的反应性高于所报道的茂金属配合物的反应性。本文讨论了由 1,1'-二茂铁二酰胺配体支持的 η2(N,C)-吡啶基钪配合物与乙烯、2-丁炔和 1,3-丁二烯的反应。
• Dearomatization Reactions of N-Heterocycles Mediated by Group 3 Complexes
  作者：Kevin L. Miller、Bryan N. Williams、Diego Benitez、Colin T. Carver、Kevin R. Ogilby、Ekaterina Tkatchouk、William A. Goddard、Paula L. Diaconescu

  DOI：10.1021/ja908489p

  日期：2010.1.13

  ligand are reactive toward aromatic N-heterocycles by mediating their coupling and, in a few cases, the cleavage of their C-N bonds. When these complexes reacted with 2,2'-bipyridine or isoquinoline, they facilitated the alkyl migration of the benzyl ligand onto the pyridine ring, a process accompanied by the dearomatization of the N-heterocycle. The products of the alkyl-transfer reactions act as hydrogen

  由二茂铁二酰胺配体支持的第 3 族 (Sc, Y, Lu, La) 苄基复合物通过介导它们的偶联以及在少数情况下其 CN 键的断裂对芳香族 N-杂环具有反应性。当这些配合物与 2,2'-联吡啶或异喹啉反应时，它们促进了苄基配体的烷基迁移到吡啶环上，这一过程伴随着 N-杂环的脱芳构化。在芳族 N-杂环、酮和偶氮苯存在下，烷基转移反应的产物充当氢供体。实验和计算研究表明，氢转移是通过协同机制发生的。还报道了脱芳构化的、烷基取代的异喹啉配合物的有趣歧化反应。
• Ring-Opening Reactions of Aromatic N-Heterocycles by Scandium and Yttrium Alkyl Complexes
  作者：Colin T. Carver、Paula L. Diaconescu

  DOI：10.1021/ja802728k

  日期：2008.6.18

  The C-N bond in aromatic N-heterocycles is a strong bond, its cleaving involving mostly examples of metal-element multiple bonds. We report on the C-C coupling of two molecules of an aromatic N-heterocycle mediated by scandium and yttrium benzyl complexes supported by a ferrocene 1,1'-diamide ligand. The reaction with 1-methylimidazole leads, ultimately, to the formation of a ring-opened imidazole

  芳族 N-杂环中的 CN 键是一种强键，其断裂主要涉及金属元素多重键的例子。我们报告了由二茂铁 1,1'-二酰胺配体支持的钪和钇苄基配合物介导的两个芳香族 N-杂环分子的 CC 耦合。与 1-甲基咪唑的反应最终导致形成与 1-甲基咪唑片段偶联的开环咪唑，该结构显示双键的扩展共轭。实验证据与这些转换中仅涉及 sigma 键一致。
• Group 3 Metal Complexes of Radical-Anionic 2,2′-Bipyridyl Ligands
  作者：Bryan N. Williams、Wenliang Huang、Kevin L. Miller、Paula L. Diaconescu

  DOI：10.1021/ic101493k

  日期：2010.12.20

  A new method for generating group 3 metal complexes containing radical-anionic 2,2′-bipyridyl (bipy) ligands is described that relies on hydrogen-atom abstraction from dearomatized biheterocyclic complexes. This method does not involve electron transfer to neutral 2,2′-bipyridyl or salt metathesis between the lithium salt of the 2,2′-bipyridyl radical anion and group 3 metal halides. The new metal

  描述了一种新的生成包含自由基-阴离子2,2'-联吡啶（bipy）配体的3族金属配合物的新方法，该方法依赖于脱芳香化的双杂环配合物的氢原子抽象。该方法不涉及电子转移至中性的2,2'-联吡啶或2,2'-联吡啶基阴离子的锂盐与第3族金属卤化物之间的盐复分解。新型金属配合物的特征在于单晶X射线衍射，电子顺磁共振和吸收光谱。密度泛函理论（DFT）计算用于探测这些化合物的电子结构。所有这些方法都支持所提出的所有联吡啶化合物中联吡啶的自由基-阴离子特性。