(+/-)-trans-N,N'-bis(salicylidene)-1,2-cyclohexanediaminenickel(II) | 336624-80-7

• 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: (+/-)-trans-N,N'-bis(salicylidene)-1,2-cyclohexanediaminenickel(II)
• 英文别名: [Ni((+/-)-trans-N,N'-bis(salicylidene)-1,2-cyclohexanediamine)]；N,N'-1,2-cyclohexyl-1,2-diyl-bis(salicylideneiminate)nickel(II)；[nickel(II)(salhd)]；[Ni(salhd)]
• CAS: 336624-80-7；344346-07-2；30954-65-5；63038-66-4
• 化学式: C₂₀H₂₀N₂NiO₂
• 分子量: 379.081
• InChiKey: MYZCRYKBWIOIQD-JKBLJYNNSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (+/-)-trans-N,N'-bis(salicylidene)-1,2-cyclohexanediaminenickel(II) 、 一氧化碳 以 N,N-二甲基甲酰胺 为溶剂， 生成
  参考文献：
  名称：

  Reductive electrochemical study of Ni(II) complexes with N2O2 Schiff base complexes and spectroscopic characterisation of the reduced species. Reactivity towards CO

  摘要：

  Reductive electrochemical properties of series of nickel(II) complexes with salen ligands, which have different diimine bridges and substituents in the aldehyde moiety have been studied in several solvents (CH3CN, dmf and (CH3)(2)SO). In order to assess the relative importance of the Ni(I) and Ni(II) anion radical species, the reduced species have been characterised by combining EPR and UV-Vis spectroscopy. The results have shown that complexes with aliphatic diimine bridges are reduced to four-coordinate Ni(l) species with a B-1g (d(xy))(1) ground state, whereas those with aromatic diimine bridges are reduced to square-planar Ni(II) anion radical species that rapidly dimerise. None of the reduced species was found to bind pyridine, imidazole and triphenylphosphine, but in the presence of the stronger pi-acceptor ligand CO, new Ni(I) species were formed that, and on the basis of EPR data, can be formulated as five-coordinate complexes with a B-1g (d(xy))(1) ground state, [NiL.CO](-). These new species are more stable than the parent complexes as confirmed by the more positive E-1/2 values as a consequence of the extensive pi delocalisation M --> CO. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(02)01025-2
• 作为产物：
  描述：

  rac-trans-N,N'-bis(salicylidene)-1,2-cyclohexanediamine 、 nickel(II) acetate tetrahydrate 以 乙醇 、 水 为溶剂， 反应 2.0h， 以75%的产率得到(+/-)-trans-N,N'-bis(salicylidene)-1,2-cyclohexanediaminenickel(II)
  参考文献：
  名称：

  还原和氧化的电化学研究和光谱性质的镍（II）配合物用N 2个ö 2个夫碱从（±）衍生的-反式- N，N' -双（亚水杨基）-1,2-环己二胺

  摘要：

  -循环伏安法，计时，计时库仑，控制电位电解和UV VIS在配体和Ni（II）络合物与（±）的调查中使用的反式- N，N' -双（亚水杨基）-1,2-环己烷二胺取代在沃尔托具有叔丁基和/或甲氧基的酚盐阴离子的-和/或对位。显示了配体的不可逆还原和氧化。没有观察到溶剂对络合物还原的影响，这导致形成Ni（I）络合物，但是，证明了溶剂和酚盐阴离子取代基对氧化过程的影响。（CH 3）2中的阳极过程SO总是产生合适的Ni（III）-酚盐配合物。氧化沃尔托-和对位-在CH取代的配合物2氯2所导致的Ni（II） -单-苯氧基的基团，其经历离域，并且随后被氧化为镍（II） -双-苯氧基的基团。自由基的最后氧化步骤会产生长寿命的Ni（II）-双-苯氧鎓阳离子。没有取代基的复合物对位-和/或沃尔托具有形成位置的Ni（II） -单-苯氧基的基团二聚经历- 。研究了电极过程的机理，并对还原过程和I st过程的D和E

  DOI：

  10.1016/j.electacta.2013.12.073

文献信息

• Photochemistry of nickel salen based complexes and relevance to catalysis
  作者：Baltazar de Castro、Rita Ferreira、Cristina Freire、Hermenegildo García、Emilio J. Palomares、María J. Sabater

  DOI：10.1039/b108436d

  日期：2002.4.2

  A series of four nickel salen complexes have been synthesised and their photochemical properties studied. These complexes emit in hexane at λem 580 nm with similar quantum efficiencies. Fluorescence decay occurs on the nanosecond time scale and its intensity is quenched by oxygen except for the complex with the shortest lifetime. For all complexes laser flash photolysis in CH2Cl2 or hexane generates a transient (lifetime on the μs time scale) that was assigned to a Ni-to-ligand electron transfer triplet excited state. In an attempt to show the relevance of photochemical data to catalysis, epoxidation of β-methylstyrene was carried out in the presence of the four complexes. It was found that the activity of the complexes correlates with the lifetime of the triplet charge-separated state. This relationship was interpreted as reflecting the intrinsic stability of the oxidised Ni ion in the different complexes, which is the common link between the photochemical and catalytic experiments.

  一系列四种镍Salen配合物已被合成并研究了它们的光化学性质。这些配合物在己烷中于580 nm的发射波长处具有相似的量子产率。荧光衰减发生在纳秒时间尺度上，且其强度被氧气淬灭，除了寿命最短的配合物。在甲基氯或己烷中的激光闪光光解实验对于所有配合物产生了一个寿命在微秒时间尺度的瞬态产物，该瞬态被归因于一种镍到配体的电子转移三重激发态。为了展示光化学数据与催化之间的相关性，在四种配合物的存在下进行了β-甲基苯乙烯的环氧化反应。研究发现，配合物的活性与三重电荷分离态的寿命相关。这种关系被解释为反映了不同配合物中氧化态镍离子的内在稳定性，这是光化学和催化实验之间的共同联系。
• A Straightforward Electrochemical Approach to Imine- and Amine-bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State
  作者：Michael R. Chapman、Susan E. Henkelis、Nikil Kapur、Bao N. Nguyen、Charlotte E. Willans

  DOI：10.1002/open.201600019

  日期：2016.8

  are diverse, with the route chosen being dependent upon many factors such as metal–ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal–salen/salan complexes which comprise diverse metal–ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes

  制备有机金属和配位化合物（例如希夫碱配合物）的合成方法多种多样，所选择的路线取决于许多因素，例如金属-配体组合和金属氧化态。在这项工作中，我们表明电化学方法可用于合成各种金属-salen/salan配合物，其中包含不同的金属-配体组合和氧化态。通过在温和环境条件下制备 34 种复合物，已证明了其广泛的应用。通过简单修改反应条件，可以实现对金属氧化态（M II/III/IV ，其中 M=Fe、Mn）前所未有的控制。沿着这条路线，描述了一个通用的协议转换，它允许获得分析纯的 Fe II/III –salen 配合物。还提出了调节电化学势、Mn/Ni 合金的选择性金属化，专门以高产率提供 Mn II/IV –salen 配合物。
• Warmuth, Ruth; Elias, Horst, Inorganic Chemistry, 1991, vol. 30, # 26, p. 5027 - 5032
  作者：Warmuth, Ruth、Elias, Horst

  DOI：——

  日期：——