NiCl₂(6,6′-dimethyl-2,2′-bipyridine) | 871656-24-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: NiCl₂(6,6′-dimethyl-2,2′-bipyridine)
• 英文别名: NiCl₂dmbpy；NiCl₂(6,6'-Me₂bpy)；[Ni^II(6,6'-dimethyl-2,2'-bipyridine)Cl₂]；dichloro(6,6'-dimethyl-2,2'-bipyridyl)nickel(II)；dichloronickel;2-methyl-6-(6-methylpyridin-2-yl)pyridine
• CAS: 871656-24-5
• 化学式: C₁₂H₁₂Cl₂N₂Ni
• 分子量: 313.837
• InChiKey: YTEYPXDIVKCIQG-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.14
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6,6'-二甲基-2,2'-联吡啶 、 NiCl₂(6,6′-dimethyl-2,2′-bipyridine) 在 2,6-二甲基吡啶 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  Two-Electron HCl to H₂ Photocycle Promoted by Ni(II) Polypyridyl Halide Complexes

  摘要：

  Photochemical HX splitting requires the management of two protons and the execution of multielectron photoreactions. Herein, we report a photoinduced two-electron reduction of a polypyridyl Ni(II) chloride complex that provides a route to H-2 evolution from HCl. The excited states of Ni complexes are too short to participate directly in HX activation, and hence, the excited state of a photoredox mediator is exploited for the activation of HX at the Ni(II) center. Nanosecond transient absorption (TA) spectroscopy has revealed that the excited state of the polypyridine results in a photoreduced radical that is capable of mediating HX activation by producing a Ni(I) center by halogen-atom abstraction. Disproportionation of the photogenerated Ni(I) intermediate affords Ni(II) and Ni(0) complexes. The Ni(0) center is capable of reacting with HX to produce H-2 and the polypyridyl Ni(II) dichloride, closing the photocycle for H-2 generation from HCl.

  DOI：

  10.1021/ja408787k
• 作为产物：
  描述：

  氯化镍二甲氧基乙烷 、 新铜试剂 以 四氢呋喃 为溶剂， 以97%的产率得到NiCl₂(6,6′-dimethyl-2,2′-bipyridine)
  参考文献：
  名称：

  Two-Electron HCl to H₂ Photocycle Promoted by Ni(II) Polypyridyl Halide Complexes

  摘要：

  Photochemical HX splitting requires the management of two protons and the execution of multielectron photoreactions. Herein, we report a photoinduced two-electron reduction of a polypyridyl Ni(II) chloride complex that provides a route to H-2 evolution from HCl. The excited states of Ni complexes are too short to participate directly in HX activation, and hence, the excited state of a photoredox mediator is exploited for the activation of HX at the Ni(II) center. Nanosecond transient absorption (TA) spectroscopy has revealed that the excited state of the polypyridine results in a photoreduced radical that is capable of mediating HX activation by producing a Ni(I) center by halogen-atom abstraction. Disproportionation of the photogenerated Ni(I) intermediate affords Ni(II) and Ni(0) complexes. The Ni(0) center is capable of reacting with HX to produce H-2 and the polypyridyl Ni(II) dichloride, closing the photocycle for H-2 generation from HCl.

  DOI：

  10.1021/ja408787k
• 作为试剂：
  描述：

  3-[tert-butyl(dimethyl)silyl]oxybutyl 4-methylbenzenesulfonate 、 叔丁基异氰酸酯 在 锰 、 三甲基氯硅烷 、 vitamin B₁₂ 、 NiCl₂(6,6′-dimethyl-2,2′-bipyridine) 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以61%的产率得到
  参考文献：
  名称：

  Ni / Co-双重催化体系将甲苯磺酸烷基酯与异氰酸酯还原酰胺化。

  摘要：

  公开了使用Ni / Co-双催化体系对甲苯磺酸烷基酯与异氰酸酯的还原酰胺化。该方法在温和条件下有效地进行，得到相应的烷基酰胺。值得注意的是，该协议可以区分两个甲苯磺酸烷基酯部分的空间环境，从而在较小的位点实现区域选择性单酰胺化。

  DOI：

  10.1039/c9cc09377j

文献信息

• Activation of chlorobenzene with Ni(0) <i>N</i>,<i>N</i>-chelates — A remarkably profound effect of a minuscule change in ligand structure
  作者：William J Marshall、Vladimir V Grushin

  DOI：10.1139/v05-022

  日期：2005.6.1

  Activation of the C—Cl bond of chlorbenzene with [(COD)₂Ni] and a bidentate N,N-ligand such as N,N,N′,N′-tetramethylethylenediamine (tmeda) and 2,2′-bipyridyl (bipy) has been reported to produce σ-phenyl complexes [(tmeda)Ni(Ph)Cl] (1) and [(bipy)Ni(Ph)Cl], respectively. However, in sharp contrast, we found that similar reactions involving almost the identical ligands N,N,N′,N′-tetraethylethylenediamine (teeda) and 6,6′-dimethyl-2,2′-bipyridyl (6,6′-Me₂bipy) resulted in homocoupling and the formation of non-organometallic dichlorocomplexes [(teeda)NiCl₂] and [(6,6′-Me₂bipy)NiCl₂]. The latter two compounds and 1 were characterized by single-crystal X-ray diffraction data. The remarkable change in the reaction outcome points to its extremely high sensitivity to minor alterations in the structure of the stabilizing N,N-ligand. In contrast, analogous reactions of [Pd(dba)₂] with PhI in the presence of teeda or 1,2-dipiperidinoethane (dpe) produced the expected σ-phenyl complexes [(teeda)Pd(Ph)I] and [(dpe)Pd(Ph)I], much like the previously reported reaction with tmeda.Key words: C-Cl activation, zerovalent nickel complexes, N,N-ligands, oxidative addition, homocoupling, X-ray analysis.

  氯苯的C-Cl键与[(COD)₂Ni]和双齿N,N-配体（如N,N,N′,N′-四甲基乙二胺（tmeda）和2,2′-联吡啶（bipy））的活化已被报道，产生σ-苯基配合物[(tmeda)Ni(Ph)Cl]（1）和[(bipy)Ni(Ph)Cl]。然而，与之形成鲜明对比的是，我们发现类似反应涉及几乎相同的配体N,N,N′,N′-四乙基乙二胺（teeda）和6,6′-二甲基-2,2′-联吡啶（6,6′-Me₂bipy）导致同偶联和非有机金属二氯化物配合物[(teeda)NiCl₂]和[(6,6′-Me₂bipy)NiCl₂]的形成。后两种化合物和1通过单晶X射线衍射数据进行了表征。反应结果的显著变化表明其对N,N-配体稳定结构中微小变化的极高敏感性。相比之下，[Pd(dba)₂]与PhI在teeda或1,2-二哌啶乙烷（dpe）存在的情况下的类似反应产生了预期的σ-苯基配合物[(teeda)Pd(Ph)I]和[(dpe)Pd(Ph)I]，类似于先前报道的与tmeda的反应。关键词：C-Cl活化，零价镍配合物，N,N-配体，氧化加成，同偶联，X射线分析。
• 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。
• Taming the Lewis Superacid Al(ORF)3 (RF=C(CF3)3): DFT Guided Identification of the “Stable yet Reactive” Adduct SiPr2→Al(ORF)3; Its Use as ORF‐ Abstractor from a “Ni‐ORF” complex.
  作者：Julien Petit、Julien Babinot、Nathalie Saffon、Lionel Magna、Nicolas Mézailles

  DOI：10.1002/chem.202203912

  日期：——

  A predictive DFT study of L→Al(ORF)3 (L=Lewis bases) adducts allowed the identification of (iPr2S)→Al(ORF)3 as a “stable yet reactive” adduct, able to act as a masked Lewis superacid. It provides a novel strategy to use M-ORF/L→Al(ORF)3 couples to generate catalytically active M+ centers featuring weakly coordinating aluminate counter anion.

  L→Al ( ORF ) 3 ( L=Lewis bases )加合物的预测性 DFT 研究允许将 ( i Pr 2 S)→Al(ORF) 3鉴定为“稳定但反应性”加合物，能够充当掩蔽路易斯超强酸。它提供了一种利用M-ORF/L→Al(ORF) 3对生成具有弱配位铝酸盐抗衡阴离子的催化活性M+中心的新策略。
• Two-Electron HCl to H₂ Photocycle Promoted by Ni(II) Polypyridyl Halide Complexes
  作者：David C. Powers、Bryce L. Anderson、Daniel G. Nocera

  DOI：10.1021/ja408787k

  日期：2013.12.18

  Photochemical HX splitting requires the management of two protons and the execution of multielectron photoreactions. Herein, we report a photoinduced two-electron reduction of a polypyridyl Ni(II) chloride complex that provides a route to H-2 evolution from HCl. The excited states of Ni complexes are too short to participate directly in HX activation, and hence, the excited state of a photoredox mediator is exploited for the activation of HX at the Ni(II) center. Nanosecond transient absorption (TA) spectroscopy has revealed that the excited state of the polypyridine results in a photoreduced radical that is capable of mediating HX activation by producing a Ni(I) center by halogen-atom abstraction. Disproportionation of the photogenerated Ni(I) intermediate affords Ni(II) and Ni(0) complexes. The Ni(0) center is capable of reacting with HX to produce H-2 and the polypyridyl Ni(II) dichloride, closing the photocycle for H-2 generation from HCl.