bis(thiosalicylaldehydato)nickel(II) | 19621-40-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(thiosalicylaldehydato)nickel(II)
• 英文别名: 2-formylbenzenethiolate;nickel(2+)
• CAS: 19621-40-0
• 化学式: C₁₄H₁₀NiO₂S₂
• 分子量: 333.054
• InChiKey: NQYVDVWIKIOAJA-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：

  bis(thiosalicylaldehydato)nickel(II) 生成
  参考文献：
  名称：

  Garnovskii, A. D.; Gerbeleu, N. V.; Kochin, S. G., Doklady Chemistry, 1989, vol. 306, p. 167 - 170

  摘要：

  DOI：
• 作为产物：
  描述：

  2-硫代水杨醛 、 nickel diacetate 以 not given 为溶剂， 生成 bis(thiosalicylaldehydato)nickel(II)
  参考文献：
  名称：

  亚核的组装和双金属螺旋的金属转移

  摘要：

  仅作为螺旋体提供：带有以前难以接近的N，S-N，S配体的双核锌和镍配合物是在带有两个2-硫代对苯二甲醛配体和4,4'-二氨基二苯甲烷的配合物的亚组分自组装反应中获得的。两种络合物均通过重金属化作用与Pd（OAc）2反应，生成双核钯络合物（请参见方案）。

  DOI：

  10.1002/anie.201002776

文献信息

• Reversible Formation and Transmetalation of Schiff-Base Complexes in Subcomponent Self-Assembly Reactions
  作者：Dennis Lewing、Hannah Koppetz、F. Ekkehardt Hahn

  DOI：10.1021/acs.inorgchem.5b01334

  日期：2015.8.3

  Dinuclear complexes [Zn2(NS,NS)2] 3 and [Ni2(NS,NS)2] 6 bearing Schiff-base ligands featuring two NS donor groups were obtained in subcomponent self-assembly reactions using nickel or zinc as template metals. Several transmetalation reactions starting from 3 or 6 yielded the complexes [Pd2(NS,NS)2] 4 and [Co2(NS,NS)2] 5, and their molecular structures were determined by X-ray diffraction. Starting

  在以镍或锌为模板金属的亚组分自组装反应中，获得了具有两个NS供体基团的席夫碱配体的双核配合物[Zn 2（NS，NS）2 ] 3和[Ni 2（NS，NS）2 ] 6。。从3或6开始的几次金属转移反应产生了[Pd 2（NS，NS）2 ] 4和[Co 2（NS，NS）2 ] 5的配合物，并通过X射线衍射确定了它们的分子结构。从单核络合物[Ni（NS / NOH）2 ]开始9设有一个协调NS席夫碱和游离NOH席夫碱，完全观察到可逆热力学控制亚胺键的形成，导致复杂的[镍2（NS，NS）2 ] 6和自由席夫碱基配体NOH，NOH 10。
• Nickel(II) complexes with N2OS and N2S2 co-ordination spheres: reduction and spectroscopic study of the corresponding Ni(I) complexes
  作者：Lígia Gomes、Eulália Pereira、Baltazar de Castro

  DOI：10.1039/a908330h

  日期：——

  Nickel(II) complexes with Schiff-bases obtained by condensation of 1,3-propanediamine with salicylaldehyde and thiosalicylaldehyde, which present a N2OS or N2S2 co-ordination sphere, were synthesized and studied. The molecular and crystal structure of the asymmetric complex [2-(3-[(3,5-dichloro-2-hydroxyphenyl)methyleneamino]propyl}iminomethylene)benzenethiolato-O,N,N′,S]nickel(II) [Ni(t-salCl2salpd)] has been determined by X-ray crystallography and shows a tetrahedrally distorted square-planar co-ordination geometry for the nickel center. The complexes were characterized by spectroscopic and electrochemical techniques and the results were used to assess the influence of the donor-atoms on their chemical properties. The results obtained show that the compounds may be reduced, either chemically or electrochemically, to Ni(I) complexes. Reduction potentials were found to be strongly dependent on the tetrahedral distortion of the Ni(II) complexes. EPR parameters for Ni(I) complexes, although not very sensitive to ligand substituents, show a regular dependence on the co-ordination set and the tetrahedral distortion of the complexes.

  研究人员合成并研究了由 1,3-丙二胺与水杨醛和硫代水杨醛缩合得到的具有 N2OS 或 N2S2 配位层的希夫碱镍(II)配合物。通过 X 射线晶体学确定了不对称配合物 [2-(3-[(3,5-二氯-2-羟基苯基)亚甲基氨基]丙基}亚氨基亚甲基)苯硫酚-O,N,N′,S]镍（II）[Ni(t-salCl2salpd)] 的分子和晶体结构，并显示出镍中心的四面体畸变方平面配位几何。通过光谱和电化学技术对这些复合物进行了表征，并利用表征结果评估了供体原子对其化学性质的影响。研究结果表明，这些化合物可以通过化学或电化学方法还原成 Ni(I) 复合物。还原电位与 Ni(II) 复合物的四面体畸变密切相关。镍（I）络合物的 EPR 参数虽然对配体取代基不太敏感，但却显示出对配位集和络合物四面体畸变的规律性依赖。
• Garnovskii, A. D.; Mistryukov, A. E.; Kochin, S. G., Russian Journal of Inorganic Chemistry, 1992, vol. 37, p. 648 - 653
  作者：Garnovskii, A. D.、Mistryukov, A. E.、Kochin, S. G.、Sergienko, V. S.、Vasil'chenko, I. S.、et al.

  DOI：——

  日期：——
• Changes in Geometries and Spin States of Thiolato-Schiff Base NiN2S2 Complexes Containing N,N'-Biphenyl Backbones
  作者：Henrik Frydendahl、Hans Toftlund、Jan Becher、Jennifer C. Dutton、Keith S. Murray、Lucille F. Taylor、Oren P. Anderson、Edward R. T. Tiekink

  DOI：10.1021/ic00121a027

  日期：1995.8

  Four new 5-formylpyrazole-based thiolato Schiff base nickel(II) complexes (1-4) have been synthesized from the corresponding ligands and nickel(II) acetate. A new 2-mercaptobenzaldehyde Schiff base nickel(II) complex (5) has been synthesized by two routes. X-ray structural analyses on three of the complexes showed the following: 1, chemical formula C26H26N6S2Ni, monoclinic, space group P2(1)/n with a = 10.438(2) Angstrom, b = 12.450(3) Angstrom, c = 19.616(3) Angstrom, beta = 94.33(1)degrees, Z = 4, and R = 0.044 for 3365 reflections; 4, chemical formula C34H26N6S2Ni, monoclinic, space group C2/c with a = 19.242(3) Angstrom, b = 9.757(2) Angstrom, c = 19.691(3) Angstrom, beta = 125.84(1)degrees, Z = 4, and R = 0.032 for 2206 reflections; 5, chemical formula C28H22N2S2Ni, monoclinic, space group C2/c with a = 25.230(4) Angstrom, b = 11.098(2) Angstrom, c = 17.287(8) Angstrom, beta = 98.46(3)degrees, Z = 8, and R = 0.047 for 1912 reflections. The coordination geometry in 1 is distorted tetrahedral while in 4 and 5 it is close to cis-square planar despite the influence of the (6,6'-dimethyl)biphenyl group in the tetradentate ligand backbone. The bond distances are as follows. Ni-S: 1, 2.239(1), 2.243(1) Angstrom; 4, 2.185(1) Angstrom; 5, 2.152(2), 2.184 (2) Angstrom. Ni-N: 1, 1.963(2), 1.968(2) Angstrom; 4, 1.927(2); 5, 1.931(5), 1.917(6) Angstrom. The distortions from tetrahedral to planar geometry are manifest in some interesting changes in dihedral angles and donor atom ''bite'' distances. The magnetic susceptibilities were measured in the temperature range 4.2-300 K for 1-5. The susceptibilities of 1 and 2 could be fitted well to a simple axial spin Hamiltonian with S = 1, D = 34 cm(-1) and S = 1, D = 53 cm(-1), respectively. Complexes 3-5 are diamagnetic and showed only small temperature-independent paramagnetic susceptibilities. Although no temperature-induced spin changes were observed for solids of 1-4, they all showed a (1)A(lg) reversible arrow T-3(1) equilibrium in chloroform solutions. Each of complexes 1-5 show LF, CT, and intraligand spectral features in the spectral region 5,000 - 40,000 cm(-1). Bands assigned to the high-spin and low-spin forms are observed separately. The thermodynamic parameters for the high-spin reversible arrow low-spin equilibria in chloroform solutions were obtained by using the Evans method, variable-temperature H-1 NMR spectra, and variable-temperature electronic spectra. Complexes 1-4 exhibit equilibrium constants K-eq (=N-HS/N-LS) in the range of 0.456-0.080.
• Garnowskiii A. D., Wasiltschenko I. S., Mistrjukow A. E., Kotschin S. G.,+, Zh. obshh. khimii, 63 (1993) N 5, S 1144-1154
  作者：Garnowskiii A. D., Wasiltschenko I. S., Mistrjukow A. E., Kotschin S. G.,+

  DOI：——

  日期：——