[Co(2,6-bis(2,6-diisopropylphenyliminoethyl)pyridine)(H)] | 763104-47-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: [Co(2,6-bis(2,6-diisopropylphenyliminoethyl)pyridine)(H)]
• 英文别名: 2,6-[2,6-(iPr)2C6H3NCMe]2C5H3NCoH；[Co(hydride)(2,6-(MeCN(2,6-(CHMe2)2C6H3))2C5H3N)]
• CAS: 763104-47-8
• 化学式: C₃₃H₄₄CoN₃
• 分子量: 541.726
• InChiKey: KPFWHCPSLYTRRP-DGOWAXEKSA-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：

  [Co(2,6-bis(2,6-diisopropylphenyliminoethyl)pyridine)(H)] 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  钴（I）烷基配合物与1-烯烃之间β-H转移的实验与计算研究

  摘要：

  双（亚氨基）吡啶钴（I）烷基络合物通过β-氢转移与1-烯烃反应，为研究聚合和低聚催化中常见的链转移过程提供了模型反应。描述了空间效应对反应速率的影响。理论模型在很大程度上与实验确定的结构相符，提供了所涉及物种的更详细视图，并且与观察到的反应性一致。实验和理论均支持涉及氢化钴中间体的逐步途径。

  DOI：

  10.1021/om049581h
• 作为产物：
  描述：

  以 氘代苯 为溶剂， 生成 [Co(2,6-bis(2,6-diisopropylphenyliminoethyl)pyridine)(H)]
  参考文献：
  名称：

  钴（I）烷基配合物与1-烯烃之间β-H转移的实验与计算研究

  摘要：

  双（亚氨基）吡啶钴（I）烷基络合物通过β-氢转移与1-烯烃反应，为研究聚合和低聚催化中常见的链转移过程提供了模型反应。描述了空间效应对反应速率的影响。理论模型在很大程度上与实验确定的结构相符，提供了所涉及物种的更详细视图，并且与观察到的反应性一致。实验和理论均支持涉及氢化钴中间体的逐步途径。

  DOI：

  10.1021/om049581h

文献信息

• Radical Mechanisms in the Reaction of Organic Halides with Diiminepyridine Cobalt Complexes
  作者：Di Zhu、Ilia Korobkov、Peter H. M. Budzelaar

  DOI：10.1021/om300182c

  日期：2012.5.28

  LCo(N2) reacts with many alkyl and aryl halides RX, including aryl chlorides, to give a mixture of LCoR and LCoX in a halogen atom abstraction mechanism. Intermediacy of free alkyl and aryl radicals is confirmed by the ring-opening of cyclopropylmethyl to crotyl, and the rearrangement of 2,4,6-tBu3C6H2 to 3,5-tBu2C6H3CMe2CH2, before binding to Co. The organocobalt species generated in this way react further

  可以通过Na / Hg还原LCoCl 2或氢解LCoCH 2 SiMe 3来制备形式上为Co（0）的配合物LCo（N 2）（L = 2,6-双（2,6-二甲基苯基亚氨基乙基）吡啶）。在后一反应中，LCOH可以通过与N≡CC反应被截留6 ħ 4 -4-CL，得到LCoN═CHC 6 ħ 4 -4-CL。LCo（N 2）与许多烷基和芳基卤化物RX（包括芳基氯化物）反应，在卤素原子提取机理中得到LCoR和LCoX的混合物。游离烷基和芳基的中间体通过环丙基甲基对巴豆基的开环和2,4,6- t Bu的重排得到证实3 C 6 H 2至3,5- t Bu 2 C 6 H 3 CMe 2 CH 2，然后与Co结合。以这种方式生成的有机钴物质进一步与活化的卤化物R'X（烷基碘；烯丙基和苄基卤化物）反应）以最有可能再次是卤素提取机理的方式产生交叉偶联产物RR'。DFT研究支持为这两个步骤建议的基本途径。MeI与LCoCH
• The Electronic Structure of (Diiminopyridine)cobalt( <scp>I</scp> ) Complexes
  作者：Quinten Knijnenburg、Dennis Hetterscheid、T. Martijn Kooistra、Peter H. M. Budzelaar

  DOI：10.1002/ejic.200300569

  日期：2004.3

  square-planar (LCoR)-R-I complexes of a diiminopyridine ligand are best regarded as containing low-spin Co-II antiferromagnetically coupled to a ligand radical anion. The lowest triplet state, corresponding to a 3d(z)(2)-->pi* excitation, is calculated to be only a few kcal/mol above the ground state, and is thermally accessible. The anomalous H-1 NMR chemical shifts of the LCoR complexes are suggested to

  DFT 计算表明，二亚氨基吡啶配体的方形平面 (LCoR)-RI 配合物最好被认为含有与配体自由基阴离子耦合的低自旋 Co-II 反铁磁性。最低三重态对应于 3d(z)(2)-->pi* 激发，经计算仅比基态高几 kcal/mol，并且是热可及的。LCoR 复合物的异常 H-1 NMR 化学位移被认为是由于室温下三重态的热群所致。(C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004。
• Redox-Active Ligands and Organic Radical Chemistry
  作者：Di Zhu、Indira Thapa、Ilia Korobkov、Sandro Gambarotta、Peter H. M. Budzelaar

  DOI：10.1021/ic2002145

  日期：2011.10.17

  Knowledge about bonding in diiminepyridine (L) halide, alkyl, and dinitrogen complexes of the metals iron, cobalt, and nickel is summarized, and two new examples are added to the set: L1Ni(Me) and L1Ni(N2). Reactivity of these types of complexes is discussed in terms of organic radical chemistry. New C−C couplings with L2CoAr complexes are described and proposed to involve halide abstraction and radical

  总结了有关金属亚铁，钴和镍的二亚胺吡啶（L）卤化物，烷基和二氮配合物中的键合的知识，并向其中添加了两个新示例：L 1 Ni（Me）和L 1 Ni（N 2）。这些类型的配合物的反应性从有机自由基化学方面进行了讨论。描述和提出了具有L 2 CoAr配合物的新型C-C偶联，涉及卤化物抽象和自由基偶联。计算结果表明二亚胺吡啶配体很容易接受来自金属碳键的电子，因此有助于自由基的损失。
• Olefin hydrogenation using diimine pyridine complexes of Co and Rh
  作者：Quinten Knijnenburg、Andrew D. Horton、Harry van der Heijden、T. Martijn Kooistra、Dennis G.H. Hetterscheid、Jan M.M. Smits、Bas de Bruin、Peter H.M. Budzelaar、Anton W. Gal

  DOI：10.1016/j.molcata.2004.12.039

  日期：2005.5

  Square-planar cobalt diimine pyridine complexes LCoR (L=2,6-[RN=CMe](2)C5H3N; R=n-C6H13 for L h,,, 2,6-(i-Pr)(2)C6H3 for L dip) are active in the hydrogenation of monosubstituted and disubstituted olefins; sterically more hindered trisubstituted olefins do not react. For the (LCo)-Co-dip system, a diamagnetic hydride intermediate was observed, although a small amount of paramagnetic product is also formed upon reaction of (LCoR)-Co-dip with H-2. DFT studies suggest a traditional hydrogenation cycle starting with LCoH, except that intermediate LCo(R)(H-2) transfers a hydrogen atom directly from H-2 to the alkyl group in a sigma-bond metathesis step, without going through a discrete Co-III. intermediate. Autoclave experiments show that conversion is not linear in catalyst intake. Diffusion limitation was ruled out as an explanation, and we propose a concentration-dependent catalyst decay. At low catalyst intake conversion rates up to 2 x 104 (mol octene/mol Colbar/h) can be reached. Reducing the steric bulk at the imine positions (L-dip -> L-hex), or changing the metal from cobalt to rhodium, do not alter the activity or specificity of the hydrogenation much. For the (LCo)-Co-hex and (LRh)-Rh-dip systems, no diamagnetic products corresponding to (LCoH)-Co-dip were observed. (c) 2005 Elsevier B.V. All rights reserved.
• Investigations into the Mechanism of Activation and Initiation of Ethylene Polymerization by Bis(imino)pyridine Cobalt Catalysts:  Synthesis, Structures, and Deuterium Labeling Studies
  作者：Martin J. Humphries、Kilian P. Tellmann、Vernon C. Gibson、Andrew J. P. White、David J. Williams

  DOI：10.1021/om049032b

  日期：2005.4.1

  The activation of bis(imino)pyridine cobalt(II) precatalysts by MAO leads initially to a bis(imino)pyridine cobalt(I) cationic species with no cobalt-C(alkyl) bond into which insertion can occur. Mechanistic studies have shown that the initiation of polymerization from this species involves incorporation of alkyl groups from the cocatalyst, most likely involving attack of methide anion (from the counteranion) on a cobalt-ethylene species.