Lithium 2-lithiobenzenethiolate | 117526-82-6

• 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-lithiobenzenethiolate
• 英文别名: lithium 2-lithiothiophenolate
• CAS: 117526-82-6
• 化学式: C₆H₄Li₂S
• 分子量: 122.046
• InChiKey: APWYCTQUEYBITB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.98
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Lithium 2-lithiobenzenethiolate 在 三氯硅烷 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以11%的产率得到tris(2-mercaptophenyl)silane
  参考文献：
  名称：

  in-Cyclophanes containing second-row elements poised above aromatic rings

  摘要：

  The silicon- and phosphorus-containing cyclophanes 2 and 3 were prepared by base-promoted condensation of tris(2-mercaptophenyl)silane and tris(2-mercaptophenyl)phosphine, respectively, with 1,3,5-tris(bromomethyl)benzene. The structures of both cyclophanes were determined by X-ray crystallography. In compound 2, the distance from the apical silicon to the center of the basal aromatic ring was 3.34 angstrom, and in 3 the corresponding phosphorus to ring distance was 2.90 angstrom. The H-1 NMR spectrum of 2 was characterized by a high-field Si-H resonance (delta-1.04, 5 ppm upfield from the corresponding resonance in an acyclic model), and the IR spectrum showed a high-frequency Si-H stretching band (2457 cm-1, 280 cm-1 above the acyclic model); both features result from the proximity of the in-hydrosilane to the aromatic ring. For cyclophane 3, the C-13 NMR spectrum exhibited ''through-space'' spin-spin coupling of the phosphorus atom with the carbons of the basal aromatic ring (J(PC)(methine) = 7.5 Hz and J(PC)(quaternary) = 3.5 Hz) and in the P-31 NMR spectrum the phosphorus resonance was 32 ppm downfield from that of an acyclic model, both features suggesting an unusual electronic interaction of the phosphine with the base. Due to a strong preference for an in geometry (pyramidalization of the phosphine toward the basal ring) and the consequent steric shielding, the phosphine of 3 was quite unreactive: It was not protonated by anhydrous HBr, and even when 3 was heated in refluxing hydrogen peroxide and acetic acid, the corresponding trisulfone was obtained without formation of the phosphine oxide.

  DOI：

  10.1021/ja00007a047
• 作为产物：
  描述：

  苯硫酚 在 正丁基锂 、 四甲基乙二胺 作用下， 以 环己烷 为溶剂， 反应 24.0h， 生成 Lithium 2-lithiobenzenethiolate
  参考文献：
  名称：

  o-Lithiothiophenol equivalents. Generation, reactions and applications in synthesis of hindered thiolate ligands

  摘要：

  DOI：

  10.1021/ja00184a039

文献信息

• Heteropolytopic Arsanylarylthiolato Ligands: Cis–Trans Isomerism of Nickel(II), Palladium(II), and Platinum(II) Complexes of 1-AsPh₂-2-SHC₆H₄
  作者：Alexandra Hildebrand、Imola Sárosi、Peter Lönnecke、Luminiţa Silaghi-Dumitrescu、Menyhárt B. Sárosi、Ioan Silaghi-Dumitrescu、Evamarie Hey-Hawkins

  DOI：10.1021/ic300002p

  日期：2012.7.2

  afforded the square-planar complexes trans-[Ni(AsS)-κ2S,As}2] (1), cis-[Pd(AsS)-κ2S,As}2] (2), trans-[Pd(AsS)-κ2S,As}2] (3), and cis-[Pt(AsS)-κ2S,As}2] (4). In the cases of nickel and platinum, only one isomer was isolated. With palladium, initially the cis isomer 2 is formed and undergoes slow isomerization to the trans isomer 3 in solution. Small amounts of the trinuclear complex [PtI(1-AsPh2-μ-2-S-C6H4-κ2S

  杂多芳基硫杂芳基配体1-ASPh 2 -2-SHC 6 H 4（AsSH），PhAs（2-SHC 6 H 4）2（AsS 2 H 2）和As（2-SHC 6 H 4）3（AsS 3 H 3）已经通过锂化-亲电取代程序制备。在2：1反应ASSH用的NiCl 2 ·6H 2 O，的Na 2 [的PdCl 4 ]和[PTI 2（COD）]（COD = 1,5-环辛二烯）在净的存在3得到正方形平面络合物反式- [镍（ASS）-κ 2小号，如} 2 ]（1），顺式- [钯（ASS）-κ 2小号，如} 2 ]（2），反式- [钯（ASS）-κ 2小号，如} 2 ]（3），以及顺式- [铂（ASS）-κ 2小号，正如} 2 ]（4）。在镍和铂的情况下，仅分离出一种异构体。与钯一起，最初形成顺式异构体2，并在溶液中缓慢地异构化为反式异构体3。少量三核的络合物[PTI（1- ASPH 2 -μ-2-SC
• Synthesis of Heteropolynuclear Complexes Using New Tin(IV) Dimers. X-ray Structure of [AuSnCl(<b><i>^t</i></b>Bu)₂(SC₆H₄)(PPh₃)]
  作者：Eduardo J. Fernández、Michael B. Hursthouse、Mariano Laguna、Raquel Terroba

  DOI：10.1021/om970326p

  日期：1997.12.1

  [SnR2(SC6H4)}2] (R = Me, tBu, Ph) (1a−c). The reaction of these dimer derivatives with various [AuClL] breaks the tin-sulfur bonds, affording the heterobimetallic complexes [AuSnClR2(SC6H4)L] (L = PPh3, AsPh3, CH2PPh3) (2−4). The synthesis of [AuSnClMe2(SC6H4)}2] (5) is carried out in a similar way. The lithiated product Li2(SC6H4) can react with [AuCl(PPh3)], giving [Au2(SC6H4)(PPh3)2] (6). The molecular

  Li 2（SC 6 H 4）与[SnR 2 Cl 2 ]反应，得到双核衍生物[SnR 2（SC 6 H 4）} 2 ]（R = Me，tBu，Ph）（1a-c）。这些二聚体衍生物与各种[AuClL]的反应打破了锡-硫键，提供了异双金属配合物[AuSnClR 2（SC 6 H 4）L]（L = PPh 3，AsPh 3，CH 2 PPh 3）（2- 4）。[Au SnClMe 2（SC 6 H 4）} 2 ]（5）的合成以类似的方式进行。锂化产物Li 2（SC 6 H 4）可与[AuCl（PPh 3）]反应，得到[Au 2（SC6 H 4）（PPh 3）2 ]（6）。配合物[AuSnCl（tBu）2（SC 6 H 4）（PPh 3）]（2b）已通过X射线衍射建立，显示出四面体锡中心和由“ CS”双齿配体桥接的线性金（I）原子。
• Co-complexes of ortho-dilithiated thiophenol or 2-trimethylsilylthiophenol with lithiated TMEDA molecules: synthesis, crystal structures and theoretical studies (TMEDA = N,N,N′,N′-tetramethylethylenediamine)
  作者：Alexandra Hildebrand、Peter Lönnecke、Luminita Silaghi-Dumitrescu、Ioan Silaghi-Dumitrescu、Evamarie Hey-Hawkins

  DOI：10.1039/b511827a

  日期：——

  When an excess of nBuLi was used in the ortho-dilithiation of thiophenol or 2-trimethylsilylthiophenol in the presence of TMEDA (TMEDA = N,N,N′,N′-tetramethylethylenediamine), deprotonation of TMEDA occurred and crystals of [Li3(2-S–C6H4)(CH2MeNCH2CH2NMe2)(TMEDA)}]2 (1) or [Li4(2-S-3-SiMe3–C6H3)(CH2MeNCH2CH2NMe2)2(TMEDA)}] (2) were obtained. Molecular orbital calculations on gas-phase 1 and 2 at the DFT B3LYP/6-31G(d) level reproduce the experimental structures fairly well. In spite of the short Li⋯Li distances, total electron density representations do not support the existence of Li⋯Li interactions.

  在 TMEDA（TMEDA = N,N,Nâ²,Nâ²-四甲基乙二胺）存在下，将过量的 nBuLi 用于噻吩酚或 2-三甲基硅基噻吩酚的正交二硫化反应、TMEDA 发生去质子化反应，得到 [Li3(2-SâC6H4)(CH2MeNCH2CH2NMe2)(TMEDA)}]2 (1) 或 [Li4(2-S-3-SiMe3âC6H3)(CH2MeNCH2CH2NMe2)2(TMEDA)}] (2) 晶体。在 DFT B3LYP/6-31G(d) 水平上对气相 1 和 2 进行的分子轨道计算很好地再现了实验结构。尽管 Liâ¯Li 的距离很短，但总电子密度表示法并不支持 Liâ¯Li 相互作用的存在。
• Hypercoordinated gold (i) compounds
  作者：T. V. Baukova、L. G. Kuz'mina、A. V. Churakov、N. A. Oleinikova、P. V. Petrovskii

  DOI：10.1007/bf02498963

  日期：1998.2

  The reaction of [O(AuPPh3)(3)](+)BF4(-) with a Li,K derivative of o-cresol followed by the interaction of the reaction product with CO2 gave (triphenylphosphine)gold acetate. The reaction of ClAuPPh3 with o-LiC6H4SLi afforded (triphenylphosphine)go Id thiophenoxide. According to the data of X-ray structural analysis, the latter occurs as a dimer formed through an intermolecular secondary Au...Au bond. The reaction of this complex with diazomethane was accompanied by insertion of carbene into the Au-S bond to form a new gold complex, PhSCH2AuPPh3. The reactions with PPh3Au+BF4- or HBF4 yielded a new tetranuclear gold thiocluster, [PhS(AuPPh3)(2)](2+)(BF4-)}(2), which involves Au...Au bonds that differ in strength. The structures of the compounds obtained were established by X-ray structural analysis, H-1 and P-31 NMR spectroscopy, and FAB mass spectrometry.
• Kuz'mina; Baukova; Churakov, Russian Journal of Coordination Chemistry, 1997, vol. 23, # 4, p. 279 - 288
  作者：Kuz'mina、Baukova、Churakov、Kuz'min、Dvortsova

  DOI：——

  日期：——