[cobalt(II)dibromide(2,9-dimethyl-1,10-phenanthroline)] | 14708-25-9

• 英文名称: [cobalt(II)dibromide(2,9-dimethyl-1,10-phenanthroline)]
• 英文别名: [Co(2,9-dimethyl-1,10-phenanthroline)Br₂]；[CoBr₂(2,9-dimethyl-1,10-phenanthroline)]；[Co(neocuproine)Br₂]；[Co(dmphen)Br₂]；[CoBr₂(dmphen)]；[Co(neoc)Br₂]
• CAS: 14708-25-9
• 化学式: C₁₄H₁₂Br₂CoN₂
• 分子量: 427.064
• InChiKey: MAOGIORLVVVCMI-UHFFFAOYSA-L

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：

  [cobalt(II)dibromide(2,9-dimethyl-1,10-phenanthroline)] 、 2'-羟基苯丙酮 在 sodium methylate 作用下， 以 甲醇 、 水 为溶剂， 反应 2.0h， 以58%的产率得到[Co(2-hydroxy-propiophenone-H)(2,9-dimethyl-1,10-phenanthroline)Br]
  参考文献：
  名称：

  Different geometries of novel cobalt(II) compounds with 2-hydroxy-benzophenones and neocuproine: Crystal and molecular structures of [Co(2-hydroxy-benzophenone)2(neoc)], [Co(2-hydroxy-4-methoxybenzophenone)(neoc)Br] and [Co(neoc)Br2]·CH3OH·H2O

  摘要：

  Ten mixed-ligand Co(II) compounds with 2-hydroxy-benzophenones(ketones) and neocuproine(neoc) were synthesized and characterized by physicochemical and spectral (IR, UV-Vis) data. The cyclic voltammetry study in CH3CN gave all the expected waves for the redox processes of the metal Co(II) and the studied ligands. The X-ray diffraction study of two representative compounds proved the two different geometries, octahedral for [Co(2-hydroxy-benzophenone)(2)(neoc)] (3) and trigonal bipyramidal for [Co(2-hydroxy-4-methoxybenzophenone)(neoc)Br] (10). Additionally, the precursor compound [Co(neoc)Br-2]center dot CH3OH center dot H2O (11) was proved by (X-ray) to posses tetrahedral geometry. The molecular structure and the possible isomers of the trigonal bipyramidal complex 10 were studied by means of density functional calculations (DFT). The thermal stability was investigated by means of simultaneous TG/DTG-DTA technique in nitrogen atmosphere up to 1000 degrees C, where metallic cobalt was found as the solid residue. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.06.012
• 作为产物：
  描述：

  新铜试剂 、 cobalt(II) bromide 以 乙醇 为溶剂， 生成 [cobalt(II)dibromide(2,9-dimethyl-1,10-phenanthroline)]
  参考文献：
  名称：

  四环钴（II）与新环丙氨酸的复合物：具有潜在生物活性的单分子磁体

  摘要：

  两种单核四配位配合物[Co（dmphen）Br 2 ]和[Co（dmphen）I 2 ]（dmphen  = 2,9-二甲基-1,10-菲咯啉）的相互作用，最近据报道其表现为单分子通过光谱方法（UV-Vis，荧光和圆二色性）研究了在外加磁场中的牛（SMM）和小牛胸腺（CT）DNA的溶液。结果表明，两种配合物及其氯代类似物[Co（dmphen）Cl 2 ]都能通过嵌入与CT DNA结合，线性猝灭图获得的Stern–Volmer常数值为1.86×10 4。 –2.11×10 4 M -1。此外，拓扑异构酶I抑制研究表明，所有三种复合物在浓度为45μM时均表现出抑制活性。

  DOI：

  10.1007/s11696-017-0322-5

文献信息

• Investigating the Role of Ligand Electronics on Stabilizing Electrocatalytically Relevant Low-Valent Co(I) Intermediates
  作者：David P. Hickey、Christopher Sandford、Zayn Rhodes、Tobias Gensch、Lydia R. Fries、Matthew S. Sigman、Shelley D. Minteer

  DOI：10.1021/jacs.8b12634

  日期：2019.1.23

  ranging from hydrogen evolution to C-H functionalization. However, the use of such complexes often requires polydentate, bulky ligands to stabilize the catalytically active Co(I) oxidation state from deleterious disproportionation reactions to enable the desired reactivity. Herein, we describe the use of bidentate electronically asymmetric ligands as an alternative approach to stabilizing transient Co(I)

  钴配合物作为电催化剂在从析氢到 CH 功能化的应用中显示出巨大的潜力。然而，此类配合物的使用通常需要多齿、庞大的配体来稳定具有催化活性的 Co(I) 氧化态，以免发生有害的歧化反应，从而实现所需的反应性。在此，我们描述了使用双齿电子不对称配体作为稳定瞬态 Co(I) 物种的替代方法。使用电化学生成的 Co(I) 配合物的歧化率作为稳定性模型，我们测量了用一系列 N，N-二齿配体制备的配合物的相对稳定性。虽然 Co(I)Cl 配合物的稳定性与实验测量的热力学性质有关，与外球电子转移过程一致，发现评估的一组连接的 Co(I)Br 配合物优先被电子不对称配体稳定，证明了另一种歧化机制。这些结果使人们对有机金属配合物歧化所涉及的基本过程有了更深入的了解，并允许鉴定出有望开发新型电催化反应的钴配合物。
• Ligand and solvent effects on cobalt(I)-catalysed reactions: Alkyne dimerisation versus [2+2+2]-cyclotrimerisation versus Diels–Alder reaction versus [4+2+2]-cycloaddition
  作者：Gerhard Hilt、Wilfried Hess、Thomas Vogler、Christoph Hengst

  DOI：10.1016/j.jorganchem.2005.03.067

  日期：2005.11

  bromide complex, zinc and zinc iodide in acetonitrile. With 2–5 mol% of the cobalt catalyst at ambient temperatures 1,2,4-triphenylbenzene could be obtained in 99% yield and in excellent regioselectivity (95:5) in 10 min reaction time. Competition experiments of phenylacetylene and isoprene were performed. A preference for the cyclotrimerisation reaction was found for the diimine cobalt complex in acetonitrile

  当CoBr 2时，钴催化的苯基乙炔转化导致线性烯炔二聚产物在不存在路易斯酸的情况下，用镁将（dppe）活化。相反，在路易斯酸的存在下，环三聚反应过程是有利的。在几种测试的配体体系和溶剂中，使用由二亚胺溴化钴配合物，乙腈中的锌和碘化锌组成的催化剂体系可获得最佳结果。在室温下使用2–5 mol％的钴催化剂，可以在10分钟的反应时间内以99％的收率和出色的区域选择性（95：5）获得1,2,4-三苯苯。进行了苯乙炔和异戊二烯的竞争实验。对于乙腈中的二亚胺钴配合物，发现优先进行环三聚反应，而二氯甲烷中的钴（dppe）配合物则有利于Diels-Alder反应。
• Field‐Induced Slow Magnetic Relaxation in Mononuclear Tetracoordinate Cobalt(II) Complexes Containing a Neocuproine Ligand
  作者：Lukáš Smolko、Juraj Černák、Juraj Kuchár、Cyril Rajnák、Ján Titiš、Roman Boča

  DOI：10.1002/ejic.201700293

  日期：2017.6.30

  series of mononuclear tetracoordinate [Co(dmphen)X2] (dmphen = 2,9-dimethyl-1,10-phenantroline = neocuproine; X = Cl, Br, I) complexes have been prepared by solvothermal method. X-ray diffraction experiments have shown that they possess analogous molecular structure, even though the chlorido complex crystallizes in a different crystal system and space group. The crystal structures of the complexes are stabilized

  通过溶剂热法制备了一系列单核四配位 [Co(dmphen)X2] (dmphen = 2,9-二甲基-1,10-phenantroline = neocuproine; X = Cl, Br, I) 配合物。X 射线衍射实验表明，它们具有类似的分子结构，即使氯络合物在不同的晶系和空间群中结晶。配合物的晶体结构通过 π-π 相互作用稳定。AC 磁化率测量表明，虽然溴化物和碘化物复合物表现为场诱导的单分子磁体，显示出多种慢弛豫通道，但氯化物复合物表现出反铁磁相互作用，并且不会表现出磁化的缓慢弛豫。
• Field-induced slow relaxation of magnetization in a tetrahedral Co(ii) complex with easy plane anisotropy
  作者：Wei Huang、Tao Liu、Dayu Wu、Jiajun Cheng、Z. W. Ouyang、Chunying Duan

  DOI：10.1039/c3dt51801a

  日期：——

  The mononuclear Co(II) complex dmphCoBr (dmph = 2,9-dimethyl-1,10-phenanthroline) was obtained and X-ray structurally characterized as a distorted tetrahedron environment that is responsible for the moderately strong positive anisotropy of high spin Co(II). In combination with variable-field magnetic susceptibility data at low temperature, high-field electron paramagnetic resonance (HF-EPR) spectroscopy reveals the presence of easy-plane anisotropy (D > 0) in complex dmphCoBr. Slow magnetic relaxation effects were observed for dmphCoBr in the presence of a dc magnetic field. At very low temperatures, ac magnetic susceptibility data show the magnetic relaxation time, τ, to be temperature-independent, while above 2.4 K thermally activated Arrhenius behavior is dominated with Ueff = 22.8(8) cm−1 and τ0 = 3.7(5) × 10−10 s. Upon dilution of the complex within a matrix of the isomorphous compound dmphZnBr, ac susceptibility data reveal the individual molecular nature of the slow magnetic relaxation and indicate that the quantum tunneling pathway observed at low temperatures is likely mediated by intermolecular dipolar interactions.

  研究人员获得了单核 Co(II) 复合物 dmphCoBr（dmph = 2,9-二甲基-1,10-菲罗啉），并用 X 射线对其结构进行了表征，发现这种畸变四面体环境是高自旋 Co(II) 具有中等强度正各向异性的原因。结合低温下的变场磁感应强度数据，高场电子顺磁共振（HF-EPR）光谱揭示了复合物 dmphCoBr 中易平面各向异性（D > 0）的存在。 在直流磁场存在下，观察到 dmphCoBr 的慢磁弛豫效应。在很低的温度下，交流磁感应强度数据显示磁弛豫时间 τ 与温度无关，而在 2.4 K 以上，热激活阿伦尼乌斯行为占主导地位，Ueff = 22.8(8) cm-1 和 τ0 = 3.7(5) × 10-10 s。在同构化合物 dmphZnBr 的基质中稀释该复合物后，交流电感数据揭示了慢磁弛豫的单个分子性质，并表明在低温下观察到的量子隧道途径可能是由分子间的双极相互作用介导的。
• Investigating Oxidative Addition Mechanisms of Allylic Electrophiles with Low-Valent Ni/Co Catalysts Using Electroanalytical and Data Science Techniques
  作者：Tianhua Tang、Eli Jones、Thérèse Wild、Avijit Hazra、Shelley D. Minteer、Matthew S. Sigman

  DOI：10.1021/jacs.2c09120

  日期：2022.11.2

  the critical oxidative addition mechanism to form the π-allyl-Co/Ni complex remains unclear. Herein, we present a study to investigate this process with four catalysis-relevant complexes: Co(MeBPy)Br2, Co(MePhen)Br2, Ni(MeBPy)Br2, and Ni(MePhen)Br2. Enabled by an electroanalytical platform, Co(I)/Ni(I) species were found responsible for the oxidative addition of allyl acetate. Kinetic features of different

  由于在还原性 Co/Ni 催化的烯丙基化反应中具有独特的反应性，π-烯丙基-Co/Ni 络合物的催化作用最近引起了广泛关注。尽管在反应开发方面取得了重大成功，但形成 π-烯丙基-Co/Ni 络合物的关键氧化加成机制仍不清楚。在此，我们提出了一项研究，用四种与催化相关的配合物研究该过程：Co( Me BPy)Br 2、Co( Me Phen)Br 2、Ni( Me BPy)Br 2和 Ni( Me Phen)Br 2. 通过电分析平台，发现 Co(I)/Ni(I) 物种负责乙酸烯丙酯的氧化加成。通过线性自由能关系（Hammett 型）研究、统计建模和 DFT 计算研究来表征不同底物的动力学特征。在此过程中，提出了配位电离型过渡态，与 Tsuji-Trost 反应中 Pd(0) 介导的氧化加成具有相似的特征。计算和配体结构分析研究支持这一机制，这将为下一代催化剂的开发提供关键信息。