lithium 2-phenylthiophenolate | 131437-13-3

• 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: lithium 2-phenylthiophenolate
• 英文别名: Li(S(2-(Ph)C6H4))
• CAS: 131437-13-3
• 化学式: C₁₂H₉S*Li
• 分子量: 192.21
• InChiKey: LSYZXZUKVUXZRZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.26
• 重原子数：
  14.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [1,2-bis(diisopropylphosphino)ethane]rhodium(I) chloride dimer 、 lithium 2-phenylthiophenolate 以 正己烷 为溶剂， 以75.3%的产率得到[Rh(1,2-bis(diisopropylphosphino)ethane)(μ-SC12H9)]2
  参考文献：
  名称：

  Structural properties and inversion mechanisms of [Rh(dippe)(μ-SR)]2 complexes

  摘要：

  Several new bis-thiolate complexes of the type [Rh(dippe)(mu-SR)](2) where R = H, methyl, cyclohexyl, o-biphenyl, and phenyl, or (SR)(2)=SCH2CH2CH2S have been synthesized and characterized by NMR spectroscopy and single crystal X-ray diffraction. All [Rh(dippe)(mu-SR)](2) Complexes except [Rh(dippe)(mu-SPh)](2) exhibit bent geometries, while the orientation of the thiolato substituents changes with increasing steric bulk. H-1 and P-31 NMR spectroscopies indicate that both ring inversion and sulfur inversion occur among the members of the series, which allows them to access several isomeric forms when they are in solution. I I P NMR spectroscopy indicates that sulfur inversion in [Rh(dippe)(mu-SH)](2), [Rh(dippe)(mu-Sbiphenyl)](2), and [Rh(dippe)(mu-SPh)](2) is a non-dissociative process. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2003.11.026

文献信息

• X-ray crystal structures of a series of [MII(SR)4]2− complexes (MMn, Fe, Co, Ni, Zn, Cd and Hg) with S4 crystallographic symmetry
  作者：Amrita Silver、Stephen A. Koch、Michelle Millar

  DOI：10.1016/s0020-1693(00)87348-x

  日期：1993.3

  isostructural series of compounds, M(II) tetrathiolate complexes, [Et4N]2[M(S-2-Ph-C6H4)4]·2CH3CN (MMn, Fe, Co, Ni, Zn, Cd, Hg) are determined. The compounds crystallize in the tetragonal space group I 4 c2 (No. 120), which imposes S4 crystallographic symmetry on the [M(S-2-Ph-C6H4)4]2− anions. Each of the [M(S-2-Ph-C6H4)4]2− anions have tetragonally compressed [MS4] cores. The structures of this series of complexes

  摘要X-射线晶体结构的同构和同构结构的化合物，M（II）四硫醇盐配合物，[Et4N] 2 [M（S-2-Ph-C6H4）4]·2CH3CN（MMn，Fe，Co ，Ni，Zn，Cd，Hg）。这些化合物在I4 c2的方形空间群中结晶（第120号），这使[M（S-2-Ph- ）4] 2-阴离子具有S4晶体对称性。每个[M（S-2-Ph- ）4] 2-阴离子均具有四方压缩的[MS4]核。该系列配合物的结构增加了[M（SAr）4] 2-1 /配合物构象异构体的结构分析，这对于作为[M（II）-（S-cys）4]中心的模型具有重要意义。蛋白质。
• Single-crystal spectroscopic studies of Fe(SR)42- (R = 2-(Ph)C6H4): electronic structure of the ferrous site in rubredoxin
  作者：Matthew S. Gebhard、Stephen A. Koch、Michelle Millar、Frank J. Devlin、Philip J. Stephens、Edward I. Solomon

  DOI：10.1021/ja00005a030

  日期：1991.2

  Low-temperature single-crystal magnetic circular dichroism (MCD) and polarized absorption studies were performed on an axial ferrous rubredoxin structural model complex, [Et4N]2[Fe(SR)4] (R = 2-(Ph)C6H4). This complex was found to have a d(x2-y2) ground state with the d(z2) orbital at 1400 cm-1. A ligand field analysis of the observed and assigned E5 --> T5(2) and E5 --> GAMMA-3 transitions gives Dq = -350 cm-1, C = 2800 cm-1, and B = 620 cm-1. In contrast to ferric thiolate complexes which exhibit much larger reductions, the 70% reduction in ferrous electron repulsion parameters from the free ion values is accounted for based on standard spin restricted ligand field theory. This indicates that the inverted bonding description found for ferric complexes is not present in the ferrous complexes. Thus a large electronic relaxation takes place upon reduction which should affect redox properties of iron thiolate complexes. A calculation of the ground-state zero-field splitting based on spin-orbit coupling to the T5(2) and GAMMA-3 ligand field excited states gives D(calc) = -8.7 cm-1 which is in excellent agreement with D(exp) = -8.7 +/- 0.7 cm-1 as determined from the MCD temperature dependence. The splitting of the ferrous 3d orbitals is found to depend on the interactions with the S-Fe-sigma bonding orbital as determined by the alpha-C orientation. This effect accounts for the ground-state differences between the model complex and ferrous rubredoxin and reveals a strong dependence of the ground state on the alpha-C orientation.