2,2,2-trifluoroethoxythallium | 27619-69-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 英文名称: 2,2,2-trifluoroethoxythallium
• CAS: 27619-69-8
• 化学式: C₂H₂F₃O*Tl
• 分子量: 303.415
• InChiKey: MTDUTHKQVDCPHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.47
• 重原子数：
  7.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  23.06
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [(pentamethylcyclopentaienyl)(tricyclohexylphosphine)chlororuthenium(II)] 、 2,2,2-trifluoroethoxythallium 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Johnson, Todd J.; Huffman, John C.; Caulton, Kenneth G., Journal of the American Chemical Society, 1992, vol. 114, p. 2725 - 2726

  摘要：

  DOI：
• 作为产物：
  描述：

  2,2,2-三氟乙醇 、 thallium (I) ethoxide 以 苯 为溶剂， 以85%的产率得到2,2,2-trifluoroethoxythallium
  参考文献：
  名称：

  Johnson, Todd J.; Folting, Kirsten; Streib, William E., Inorganic Chemistry, 1995, vol. 34, # 2, p. 488 - 499

  摘要：

  DOI：

文献信息

• Coordinatively Unsaturated Ruthenium Complexes As Efficient Alkyne–Azide Cycloaddition Catalysts
  作者：Marina Lamberti、George C. Fortman、Albert Poater、Julie Broggi、Alexandra M. Z. Slawin、Luigi Cavallo、Steven P. Nolan

  DOI：10.1021/om2012425

  日期：2012.1.23

  16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azide–alkyne cycloaddition reactions that afford the 1,2,3-triazole products. The scope of the Cp*Ru(PiPr3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were

  在叠氮化物-炔烃环加成反应中研究了通式为CP * Ru（L）X（其中L =膦或N-杂环卡宾配体； X = Cl或OCH 2 CF 3）的16电子钌配合物的性能。提供1,2,3-三唑产物。研究了CP * Ru（P i Pr 3）Cl预催化剂的范围，用于末端炔烃，从而以高收率产生新的1,5-二取代的1,2,3-三唑。进行了机理研究，并揭示了许多拟议的中间体。的CP * Ru（对我镨3）（η 2 -HCCPh）氯观察和表征通过1 H，13 C，和31P NMR在273和213的K.一个罕见的例子之间的温度下Ñ，Ñ -κ 2 -phosphazide复杂中，CP *茹（κ 2 -我镨3 PN 3 BN）氯，得到充分表征，并且一个单晶X-获得了X射线衍射结构。DFT计算描述了与苯乙炔和/或苄基叠氮化物的催化反应性的完整图谱。
• Site Selectivity in Electrophilic (H⁺, CH₃⁺) Abstraction on Os(H)₂X₂(PⁱPr₃)₂
  作者：Roger Kuhlman、William E. Streib、John C. Huffman、Kenneth G. Caulton

  DOI：10.1021/ja960369h

  日期：1996.1.1

  by MeOTf into L2Os(H)2(OTf)I, then L2Os(H)2(OTf)2, a non-octahedral Lewis acid which binds H2O to form the intramolecularly hydrogen bonded L2Os(H)2(OTf)2(H2O), whose intramolecular fluxionality has been characterized (1H and 31P NMR). The complexes L2Os(H)2(ORf)2 (ORf = OCH2CF3 and OCH(CF3)2) are synthesized from L2Os(H)2Cl2 and TlORf. The X-ray structure of L2Os(H)2(OCH2CF3)2 shows evidence for O→Os

  虽然 Os(H)2X2L2 (L = PiPr3, X = Cl, Br) 的质子化 (HBF4 或 HO3SCF3 = HOTf) 或甲基化 (MeOTf) 提取卤化物并导致聚集形成 (L2OsH2)2(μ-X)3+， Os(H)2I2L2 质子化形成一种物质，其 -7.5 ppm 1H NMR 化学位移具有 H2 复合物的短 T1min 特征（或短 H/H 接触）。这也得到了 OsH3I2L2+ 共振的显着同位素扰动的支持，尽管在 OsHD2I2L2+ 中没有观察到 J(HD)。相比之下，Os(H)2I2L2 被 MeOTf 转化为 L2Os(H)2(OTf)I，然后 L2Os(H)2(OTf)2，一种非八面体路易斯酸，它与 H2O 结合形成分子内氢键的 L2O (H)2(OTf)2( )，其分子内流动性已被表征（1H 和 31P NMR）。复合物 L2Os(H)2(ORf)2 (ORf
• Quantum Exchange Coupling:  A Hypersensitive Indicator of Weak Interactions
  作者：Roger Kuhlman、Eric Clot、Claude Leforestier、William E. Streib、Odile Eisenstein、Kenneth G. Caulton

  DOI：10.1021/ja970603j

  日期：1997.10.1

  Os(H)(3)ClL2 (L = (PPr3)-Pr-i) forms a 1:1 adduct with L' = PEt3, NH3, MeCN, acetone, methanol, and THF. The case L' = PEt3 permits the dearest identification of adduct structure as pentagonal bipyramidal. For NH3 and MeCN, the respective kinetics of L' loss are measured as Delta H-double dagger = 20.7(3) and 17.6(3) kcal/mol and Delta S-double dagger = 16(1) and 14.7(9) cal/(mol K). For acetone, methanol, and THF, the following respective Delta H degrees and Delta S degrees values for L' binding are measured: Delta H degrees = -10.4(1), -6.66(8), and -5.8(2) kcal/mol; Delta S degrees = -41.8(5), -25.5(3), and -33(1) cal/(mol K). Decoalesced H-1 NMR spectra are reported for several of these Os(H)(3)ClL2L' species, and they show a variety of examples of quantum exchange coupling among the hydride ligands. The values of J(e)x are higher when L' is a more weakly-binding ligand. The quantum exchange coupling constants of Os(H)(3)XL2 (X = Cl, Br, I, OCH2CF3, OCH(CF3)(2)) in CD2Cl2, in toluene, and in methylcyclohexane show an unprecedented decrease of J with increasing temperature, which is attributed to weak formation of Os(H)(3)Cl(solvent)L-2 adducts at low temperature. For L' = CO, adduct formation leads to liberation of coordinated H-2. Excess L' = MeCN or NH3 slowly leads to formation of [Os(H)(3)L'L-2(2)]Cl; the X-ray structure for L' = NH3 is reported. Crystal data (-171 degrees C): a = 11.561(4) Angstrom, b = 14.215(5) Angstrom, c = 8.851(3) Angstrom, alpha = 97.51(2)degrees, beta = 107.73(2)degrees, gamma = 104.47(2)degrees, with Z = 2 in space group . The potential energy was calculated for exchange of 2H of OsH3X(PH3)(2)L (X = Cl with L = no ligand and PH3, X = I with L = no ligand) using effective core potential ab initio methods at the MP2 level. The site exchange is found to be energetically easier for Cl than for I, in agreement with experiment. The hydride site exchange in the seven-coordinate species OsH3Cl(PH3)(3) (a model for coordination of either ligand or solvent to Os) is found to be easier than that in the 16-electron species. No dihydrogen ligand is located on the reaction path for site exchange. The current theory which relates quantum exchange to a tunneling effect was used for calculating J(ex) as a function of temperature. The dynamic study was done using several sets of coordinates, in particular the rotation angle phi and the internuclear distance r between the exchanging H. The vibrational levels have been calculated and the symmetry of each level assigned within the permutation group in order to determine the nature of the nuclear spin function associated with each level. It is found that the rotation, phi, gives rise to the largest tunneling effect but that r cannot be neglected. The influence of the temperature, J(ex)(T), was included by a Boltzmann distribution. The results are in qualitative agreement with experiment in that quantum exchange coupling is larger in the case of Cl than in the case of I. Additional ligand L increases the value of the quantum exchange coupling mostly by lowering the activation energy for pairwise exchange.
• A chain copolymer from WCl2(PMe2Ph)4 and [TlOCH2CF3]4
  作者：Helmut Rothfuss、Kirsten Folting、Kenneth G. Caulton

  DOI：10.1016/s0020-1693(00)92322-3

  日期：1993.10

  A combination Of WCl2(PMePb)4 and [TlOCHCF3]4 crystallize from hexane solution as a 1:1 material whose structure shows it to be an alternating chain copolymer. The link between the W- and Tl-containing monomers is composed of weak Tl/Cl interactions between otherwise not significantly distorted trans-WCl2P4 octahedra and Tl4O4 cubes. The compound crystallizes as two distinct polymorphs, which differ in the Tl/Cl bond lengths and also the conformation of the phenyl substituents in the W(PMe2Ph)4 substructure. Electronic spectral data support the idea that a Tl/W adduct persists in hexane solution, and it is suggested that the binding force in both solid and solution is a weak charge transfer complexation.
• Rothfuss, Helmut; Huffman, John C.; Caulton, Kenneth G., Inorganic Chemistry, 1994, vol. 33, # 2, p. 187 - 191
  作者：Rothfuss, Helmut、Huffman, John C.、Caulton, Kenneth G.

  DOI：——

  日期：——