trans-[Pd(Fmes)2(SMe2)2] | 801319-55-1

• 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: trans-[Pd(Fmes)2(SMe2)2]
• 英文别名: trans-[Pd(2,4,6-tris(trifluoromethyl)phenyl)2(S(CH3)2)2]；[Pd(2,4,6-tris(trifluoromethyl)phenyl)2(SMe2)2]；trans-[Pd(Fmes)2(S(CH3)2)2]
• CAS: 801319-55-1
• 化学式: C₂₂H₁₆F₁₈PdS₂
• 分子量: 792.892
• InChiKey: GZEMGXKNXUXBJS-UHFFFAOYSA-N

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：

  5 5'-二甲基-2,2'-二吡啶 、 trans-[Pd(Fmes)2(SMe2)2] 以 甲苯 为溶剂， 以79%的产率得到[Pd(2,4,6-tris(trifluoromethyl)phenyl)2(4,4'-dimethyl-2,2'-bipyridine)]
  参考文献：
  名称：

  Bis(fluoromesityl) Palladium Complexes, Archetypes of Steric Crowding and Axial Protection by ortho Effect − Evidence for Dissociative Substitution Processes − Observation of ¹⁹ F− ¹⁹ F Through‐Space Couplings

  摘要：

  AbstractBisarylated complexes trans‐[Pd(Fmes)2(SR2)2] [Fmes = 2,4,6‐tris(trifluoromethyl)phenyl (fluoromesityl); SR2 = SMe2, tht; tht = tetrahydrothiophene] are precursors for various bisarylated fluoromesityl palladium(II) complexes by ligand‐substitution reactions. Boiling under reflux in acetonitrile gives the mixed complexes trans‐[Pd(Fmes)2(NCMe)(SR2)], whereas boiling under reflux in toluene leads to trans‐[PdCl2L2] (L = PMe3, tBuNC, pTol‐NC, 4‐MePy), in the presence of neutral monodentate ligands, or to (NnBu4)[trans‐Pd(Fmes)2I(SR2)] when treated with (NnBu4)I. trans‐[Pd(Fmes)2(SMe2)2] reacts with bidentate ligands, also boiling under reflux in toluene, to give [Pd(Fmes)2(L−L)] [L−L = Me2bipy, 2,2′‐biquinolyl, κ2N,N′‐OCPy2, dppm (Ph2PCH2PPh2), dppe (Ph2PCH2CH2PPh2), pte (PhSCH2CH2SPh), κ2S,N‐SPPh2Py, κ2O,N‐OPPhPy2], or the bimetallic complex [Pd(Fmes)2(μ‐1κN:1,2κO:2κN‐Py2MeCO)Pd(Fmes)(SMe2)] (characterized by X‐ray diffractometry) when treated with (OH)(CH3)CPy2. The crowding associated with two Fmes groups produces several interesting features: (1) trans complexes are preferred over cis complexes, against the expected electronic preferences; (2) the low‐temperature NMR spectra of several complexes, or the X‐ray diffraction structure of [Pd(Fmes)2(2,2′‐biquinolyl)], reveal significant structural distortions associated with steric crowding; (3) the need for boiling under reflux in the synthesis suggests a dissociative substitution mechanism, which is unknown so far for Pd; (4) some of the complexes show 19F−19F through‐space couplings. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejic.200300756
• 作为产物：
  描述：

  dichlorobis (dimethyl sulfide) palladium (II) 、 2,4,6-tris(trilfuoromethyl)phenyllithium 在 H₂O 作用下， 以 乙醚 为溶剂， 以51%的产率得到trans-[Pd(Fmes)2(SMe2)2]
  参考文献：
  名称：

  Bis(fluoromesityl) Palladium Complexes, Archetypes of Steric Crowding and Axial Protection by ortho Effect − Evidence for Dissociative Substitution Processes − Observation of ¹⁹ F− ¹⁹ F Through‐Space Couplings

  摘要：

  AbstractBisarylated complexes trans‐[Pd(Fmes)2(SR2)2] [Fmes = 2,4,6‐tris(trifluoromethyl)phenyl (fluoromesityl); SR2 = SMe2, tht; tht = tetrahydrothiophene] are precursors for various bisarylated fluoromesityl palladium(II) complexes by ligand‐substitution reactions. Boiling under reflux in acetonitrile gives the mixed complexes trans‐[Pd(Fmes)2(NCMe)(SR2)], whereas boiling under reflux in toluene leads to trans‐[PdCl2L2] (L = PMe3, tBuNC, pTol‐NC, 4‐MePy), in the presence of neutral monodentate ligands, or to (NnBu4)[trans‐Pd(Fmes)2I(SR2)] when treated with (NnBu4)I. trans‐[Pd(Fmes)2(SMe2)2] reacts with bidentate ligands, also boiling under reflux in toluene, to give [Pd(Fmes)2(L−L)] [L−L = Me2bipy, 2,2′‐biquinolyl, κ2N,N′‐OCPy2, dppm (Ph2PCH2PPh2), dppe (Ph2PCH2CH2PPh2), pte (PhSCH2CH2SPh), κ2S,N‐SPPh2Py, κ2O,N‐OPPhPy2], or the bimetallic complex [Pd(Fmes)2(μ‐1κN:1,2κO:2κN‐Py2MeCO)Pd(Fmes)(SMe2)] (characterized by X‐ray diffractometry) when treated with (OH)(CH3)CPy2. The crowding associated with two Fmes groups produces several interesting features: (1) trans complexes are preferred over cis complexes, against the expected electronic preferences; (2) the low‐temperature NMR spectra of several complexes, or the X‐ray diffraction structure of [Pd(Fmes)2(2,2′‐biquinolyl)], reveal significant structural distortions associated with steric crowding; (3) the need for boiling under reflux in the synthesis suggests a dissociative substitution mechanism, which is unknown so far for Pd; (4) some of the complexes show 19F−19F through‐space couplings. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejic.200300756

文献信息

• [Pd(Fmes)₂(tmeda)]: A Case of Intermittent CH⋅⋅⋅FC Hydrogen-Bond Interaction in Solution
  作者：Camino Bartolomé、Fernando Villafañe、Jose M. Martín-Alvarez、Jesús M. Martínez-Ilarduya、Pablo Espinet

  DOI：10.1002/chem.201203512

  日期：2013.3.11

  existence of uncommon CH⋅⋅⋅FC hydrogen‐bond interactions between methyl groups of the TMEDA ligand and ortho‐CF3 groups of the Fmes ligand. The 19F NMR spectra in CD2Cl2 at very low temperature (157 K) detect restricted rotation for the two ortho‐CF3 groups involved in hydrogen bonding, which might suggest that the hydrogen bond is responsible for this hindrance to rotation. However, a theoretical

  标题化合物[Pd（Fmes）2（TMeDA）]的X射线结构（Fmes = 2,4,6-三（三氟甲基）苯基； TMeDA = N，N，N'，N'-四甲基乙二胺）罕见的C存在 H⋅⋅⋅F 的TMEDA配体甲基基团C之间的氢键相互作用和邻位的-CF 3基团的配位体Fmes的。在非常低的温度（157 K）下，CD 2 Cl 2中的19 F NMR光谱检测到两个邻-CF 3的旋转受限制氢键涉及的基团，这可能表明氢键是造成这种旋转障碍的原因。但是，对氢键能的理论研究表明，它太弱（大约7 kJ mol -1）不足以解决观察到的旋转势垒（ΔH ≠ = 26.8 kJ mol -1），这是位阻。与TMEDA配体起皱有关，应该对大多数旋转屏障负责。在更高的温度下，旋转变得很快，这要求氢键不断被分裂和恢复，并且仅在TMEDA构象变化的脉冲之后才间歇地存在。
• Monoarylated Fluoromesitylpalladium Complexes
  作者：Camino Bartolomé、Pablo Espinet、Jose M. Martín‐Alvarez、Fernando Villafañe

  DOI：10.1002/ejic.200300229

  日期：2003.9

  [Pd(μ-Cl)(Fmes)(NCMe)]2 is generated by boiling under reflux [PdCl(Fmes)(COD)] in MeCN, and has been used to obtain various binuclear monoarylated complexes [Pd(Fmes)(μ-X)L]2 [X = Br, L = MeCN, P(o-Tol)3; X = Cl, L = CO, 4-pic, 3,5-lut, P(o-Tol)3]. Other [Pd(Fmes)(μ-X)L]2 complexes have been obtained from trans-[PdCl(Fmes)(SMe2)2] (X = Cl, L = tht, SMe2, PPh3) and from K[Pd4(Fmes)4I5] [X = I, L = P(o-Tol)3]

  单芳基化配合物 [PdCl(Fmes)(LL)] [Fmes = 2,4,6-tris(trifluoromethyl)phenyl or fluoromesityl] 和 trans-[PdCl(Fmes)L2] 已通过 [PdCL2(LL)] 的芳基化获得(LL = tmeda) 或反式 [PdCL2L2] (L = SMe2)，通过在 [Pd(μ-Cl)(Fmes)(NCMe)]2 LL = 4,4'-Me2bipy, biquinolyl 中分裂桥接氯配体(2,2'-二喹啉), OPPhPy2-N,N', (OH)(CH3)CPy2-N,N', dppe, pte [1,2-双(苯硫基)乙烷]; L = 4-pic}，或通过取代 [PdCl(Fmes)(COD)] 中的二烯烃 (L = tBuNC)。[Pd(μ-Cl)(Fmes)(NCMe)]2 和单齿配体的 1:1 比例提供 [PdCl(Fmes)(NCMe)L]