lithium p-fluorophenylthiolate | 203581-79-7

• 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 p-fluorophenylthiolate
• 英文别名: Lithium;4-fluorobenzenethiolate
• CAS: 203581-79-7
• 化学式: C₆H₄FS*Li
• 分子量: 134.103
• InChiKey: CPXLCNISPLKGMU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.26
• 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：
  2

反应信息

• 作为反应物：
  描述：

  lithium p-fluorophenylthiolate 、 trans-Os(H)Br(1,2-bis(diphenylphosphino)ethane)2 以 四氢呋喃 为溶剂， 以46%的产率得到trans-Os(H)(p-SC6H4F)(1,2-bis(diphenylphosphino)ethane)2
  参考文献：
  名称：

  Protonation Reactions of trans-M(H)(SPh)(dppe)₂ (M = Ru, Os) To Give Thiol and Dihydrogen Complexes. X-ray Crystal Structure Determination of trans-Ru(H)(SPh)(dppe)₂ and trans-[Os(H)(O₂)(dppe)₂](O₃SCF₃)

  摘要：

  The compounds trans-M(H)(SPh)(dppe)(2) (M = Ru (1Ru), Os (1Os); dppe = 1,2-bis(diphenylphosphino)ethane) are synthesized by reaction of NaSPh with trans-[Ru(H-2)(H)(dppe)(2)]BPh4 or with trans-Os(H)(Br)(dppe)2 in THF under Ar. They are characterized by H-1 and P-31 NMR, IR, FAB mass spectroscopy, elemental analyses, and cyclic voltammetry. The crystal structure determination of 1Ru verifies the trans, octahedral geometry, which is distorted by ring-ring interactions. The thiophenoxide ligand is coordinated to the metal in a bent configuration, with the phenyl ring sandwiched between two phenyl rings of one of the dppe ligands. The reaction of complexes 1 with 1 equiv of HBF4 . Et2O leads to the formation of the very reactive hydride thiol complexes trans-[M(H)-(HSPh)(dppe)(2)]BF4 (M = Ru (2Ru), Os (2Os)). Analogous complexes to 1Os and 2Os with SC6H4-4-F -F instead of SPh are also described. In all cases there is no evidence for the existence of the tautomeric dihydrogen complex trans-[M(H-2)(SAr)(dppe)(2)](+). Zn the presence of excess acid the diprotonated complex trans-[Os(H-2)(HSPh)-(dppe)(2)](BF4)(2) (3Os) is formed at 233 K where the T-1(min) of the H-2 ligand at 400 MHz is similar to 34 ms so that 0.98 less than or equal to d(HH) less than or equal to 1.24 Angstrom. Under certain conditions the labile PhSH ligand of 3Os is substituted by water to give trans[Os(H-2)(OH2)(dppe)(2)](BF4)2 (4OS). The thiol complexes 2 react rapidly with H-2(g) to give the complexes trans[M(H-2)H(dppe)(2)]BF4 (5Ru, 5Os). Complexes 3Os and 4Os also react with H-2 to give 5Os. N-2 and O-2(1 atm) displace the thiol in 2Os in CH2Cl2 to produce trans-[Os(H)(L)(dppe)(2)](+) (L eta(1)-N-2 (6Os), eta 2-O-2(7OS)). trans[Os(H)(O-2)(dppe)(2)]OTf . 3C(6)H(6) is characterized by X-ray diffraction.

  DOI：

  10.1021/ic971050g

文献信息

• Organocobalt cluster complexes XXXI. the reactions of bromo- and chloro- methylidynetricobalt nonacarbonyl with thiols and lithium thiolates
  作者：Dietmar Seyferth、Cynthia Nivert Rudie、Joseph S. Merola、Donald H. Berry

  DOI：10.1016/s0022-328x(00)90538-2

  日期：1980.3

  The action of alkanethiols on bromomethylidynetricobalt nonacarbonyl in the presence of the triethylamine gives thioesters, RSC(O)CCo3(CO)9, as principal products, but arenethiols react to give tars. A more useful reactions is that between arenethiols and ClCCo3(CO09, which gives ArSCCo3(CO)9 complexes as the principal products. The actions of lithium alkane- and arenethiolates on BrCCo3(CO)9 in hydrocarbon

  在三乙胺的存在下，链烷硫醇对溴代甲基亚炔三醇九碳羰基的作用产生硫酯，RSC（O）CCo 3（CO）9为主要产物，但芳硫醇反应生成焦油。一个更有用的反应是芳硫醇与ClCCo 3（CO0 9）之间的相互作用，从而产生ArSCCo 3（CO）9络合物作为主要产物。烷烃和芳硫醇锂在烃介质中对BrCCo 3（CO）9的作用导致形成硫酯，但在三乙胺存在下或在Co 3（CO）4（SR）5型的二乙醚溶液中形成代替。讨论了这些反应的可能机理。
• Studies of C−S Bond Cleavage Reactions of Re(V) Dithiolates:  Synthesis, Reactivity, and Mechanism
  作者：Ming Li、Arkady Ellern、James H. Espenson

  DOI：10.1021/ja0519334

  日期：2005.7.1

  A series of rhenium(V) complexes, [(X)(ReO)(dt)(PPh(3))] and [(o-SC(6)H(4)PPh(2))(ReO)(mtp)], were prepared to explore electronic effects on the C-S cleavage reaction that occurs upon reaction with PAr(3) at ambient temperature [where X = S(C(6)H(4)-p-Z) (Z = OMe, Me, H, F, Cl), OPh, Cl, and SC(2)H(5), and dt is the chelating dithiolate ligand derived from 2-(mercaptomethyl)thiophenol, 1,2-ethanedithiol

  一系列铼(V)配合物，[(X)(ReO)(dt)(PPh(3))]和[(o-SC(6)H(4)PPh(2))(ReO)(mtp) ]，准备探索在环境温度下与 PAr(3) 反应时发生的 CS 裂解反应的电子效应 [其中 X = S(C(6)H(4)-pZ) (Z = OMe, Me, H 、F、Cl)、OPh、Cl 和 SC(2)H(5)，dt 是螯合二硫醇配体，衍生自 2-(巯基甲基)苯硫酚、1,2-乙二硫醇、1,3-丙二硫醇、1、 3-丁二硫醇和 2,4-戊二硫醇]。检查了 CS 激活的范围和选择性。CS 键裂解形成具有 ReS 核心的金属环 Re(V) 配合物仅发生在具有 mtp 和 pdt 框架和 X = SAr 和 SC(2)H(5) 的配合物。反应性的差异是由于辅助配体和二硫醇配体的供体能力不同，尤其是它们的供体能力，这在 CS 激活中起着关键作用。确定了 CS 活化过程的动力学；PPh(3)
• Protonation Reactions of <i>trans</i>-M(H)(SPh)(dppe)₂ (M = Ru, Os) To Give Thiol and Dihydrogen Complexes. X-ray Crystal Structure Determination of <i>trans</i>-Ru(H)(SPh)(dppe)₂ and <i>trans</i>-[Os(H)(O₂)(dppe)₂](O₃SCF₃)
  作者：Tanya Y. Bartucz、Adina Golombek、Alan J. Lough、Patricia A. Maltby、Robert H. Morris、Ravindranath Ramachandran、Marcel Schlaf

  DOI：10.1021/ic971050g

  日期：1998.4.1

  The compounds trans-M(H)(SPh)(dppe)(2) (M = Ru (1Ru), Os (1Os); dppe = 1,2-bis(diphenylphosphino)ethane) are synthesized by reaction of NaSPh with trans-[Ru(H-2)(H)(dppe)(2)]BPh4 or with trans-Os(H)(Br)(dppe)2 in THF under Ar. They are characterized by H-1 and P-31 NMR, IR, FAB mass spectroscopy, elemental analyses, and cyclic voltammetry. The crystal structure determination of 1Ru verifies the trans, octahedral geometry, which is distorted by ring-ring interactions. The thiophenoxide ligand is coordinated to the metal in a bent configuration, with the phenyl ring sandwiched between two phenyl rings of one of the dppe ligands. The reaction of complexes 1 with 1 equiv of HBF4 . Et2O leads to the formation of the very reactive hydride thiol complexes trans-[M(H)-(HSPh)(dppe)(2)]BF4 (M = Ru (2Ru), Os (2Os)). Analogous complexes to 1Os and 2Os with SC6H4-4-F -F instead of SPh are also described. In all cases there is no evidence for the existence of the tautomeric dihydrogen complex trans-[M(H-2)(SAr)(dppe)(2)](+). Zn the presence of excess acid the diprotonated complex trans-[Os(H-2)(HSPh)-(dppe)(2)](BF4)(2) (3Os) is formed at 233 K where the T-1(min) of the H-2 ligand at 400 MHz is similar to 34 ms so that 0.98 less than or equal to d(HH) less than or equal to 1.24 Angstrom. Under certain conditions the labile PhSH ligand of 3Os is substituted by water to give trans[Os(H-2)(OH2)(dppe)(2)](BF4)2 (4OS). The thiol complexes 2 react rapidly with H-2(g) to give the complexes trans[M(H-2)H(dppe)(2)]BF4 (5Ru, 5Os). Complexes 3Os and 4Os also react with H-2 to give 5Os. N-2 and O-2(1 atm) displace the thiol in 2Os in CH2Cl2 to produce trans-[Os(H)(L)(dppe)(2)](+) (L eta(1)-N-2 (6Os), eta 2-O-2(7OS)). trans[Os(H)(O-2)(dppe)(2)]OTf . 3C(6)H(6) is characterized by X-ray diffraction.