| 166103-59-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• CAS: 166103-59-9
• 化学式: C₃₄H₂₈N₆S₂
• 分子量: 584.769
• InChiKey: AKCQGPUIQAZTDY-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  、 nickel(II) acetate tetrahydrate 以 乙醇 、 氯仿 为溶剂， 以78%的产率得到
  参考文献：
  名称：

  Changes in Geometries and Spin States of Thiolato-Schiff Base NiN2S2 Complexes Containing N,N'-Biphenyl Backbones

  摘要：

  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.

  DOI：

  10.1021/ic00121a027

文献信息

• Characterization of a pseudo-tetrahedral copper(II) complex with two thiolato and two imino donor atoms
  作者：Oren P. Anderson、Jan Becher、Henrik Frydendahl、Lucille F. Taylor、Hans Toftlund

  DOI：10.1039/c39860000699

  日期：——

  characterization of a stable copper(II) complex of a new, sterically constrained tetradentate ligand obtained from 2,2′-bis-(1-phenyl-3-methyl-5-t-butylthiopyrazol-4-ylmethyleneamino)biphenyl containing two imino and two thiolato donor atoms reveals a pseudotetrahedral CuN2S2 co-ordination array with a CuN2–CuS2 dihedral angle of 51.9° and appreciable S ⋯ S interaction; the electronic structure of this compound

  从含有两个亚氨基的2,2'-双-（1-苯基-3-甲基-5-叔丁基硫代吡唑-4-基亚甲基氨基）联苯获得的新的，空间受限的四齿配体的稳定铜（II）配合物的结构表征两个硫醇基供体原子显示出一个伪四面体CuN 2 S 2配位阵列，CuN 2 -CuS 2二面角为51.9°，且有明显的S⋯S相互作用。该化合物的电子结构与涉及铜金属蛋白中Cu–S发色团的铜中心的电子结构有关。