thallium(I) bis(trifluoromethyl)methanolate | 27619-71-2

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 英文名称: thallium(I) bis(trifluoromethyl)methanolate
• 英文别名: 1,1,1,3,3,3-hexafluoropropan-2-yloxythallium
• CAS: 27619-71-2
• 化学式: C₃HF₆OTl
• 分子量: 371.414
• InChiKey: HVNCEIPGKAFPKE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.46
• 重原子数：
  11.0
• 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：

  thallium(I) bis(trifluoromethyl)methanolate 、 1,1,1,3,3,3-Hexafluoropropan-2-olate;zirconium(4+) 以 甲苯 为溶剂， 以95%的产率得到
  参考文献：
  名称：

  有机氟与分子氟醇盐化合物中的钠和铊 (I) 结合

  摘要：

  化合物 (NaOR[sub f])[sub 4] (R[sub f] = CH(CF)[sub 3])[sub 2], Zr(OR[sub f])[sub 4] (2), Zr(OR[prime][sub f])[sub 4] (R[prime][sub f] = CMe(CF[sub 3])[sub 2]) (3), Na[sub 2]Zr(OR [sub f])[sub 6](C[sub 6]H[sub 6])[sub n]（当 n = 1 时为 4a，当 n = 2 时为 4b），和 Tl[sub 2]Zr(OR[sub f])[sub 6] (5) 已经合成并通过 IR、多核 NMR 和质谱以及（对于 1、3、4a、b 和 5）X 射线衍射结构测定进行表征。分子外围的重氟化使所有这些分子化合物都具有高度挥发性。此外，所有 X 射线结构（除了 3 的结构）都显示了许多有机氟和亲电子试

  DOI：

  10.1021/ja00065a021
• 作为产物：
  描述：

  六氟异丙醇 、 thallium (I) ethoxide 以 乙醇 为溶剂， 以80%的产率得到thallium(I) bis(trifluoromethyl)methanolate
  参考文献：
  名称：

  有机氟与分子氟醇盐化合物中的钠和铊 (I) 结合

  摘要：

  化合物 (NaOR[sub f])[sub 4] (R[sub f] = CH(CF)[sub 3])[sub 2], Zr(OR[sub f])[sub 4] (2), Zr(OR[prime][sub f])[sub 4] (R[prime][sub f] = CMe(CF[sub 3])[sub 2]) (3), Na[sub 2]Zr(OR [sub f])[sub 6](C[sub 6]H[sub 6])[sub n]（当 n = 1 时为 4a，当 n = 2 时为 4b），和 Tl[sub 2]Zr(OR[sub f])[sub 6] (5) 已经合成并通过 IR、多核 NMR 和质谱以及（对于 1、3、4a、b 和 5）X 射线衍射结构测定进行表征。分子外围的重氟化使所有这些分子化合物都具有高度挥发性。此外，所有 X 射线结构（除了 3 的结构）都显示了许多有机氟和亲电子试

  DOI：

  10.1021/ja00065a021

文献信息

• Non-oxo chemistry of manganese in high oxidation states. Part 1. Mononuclear tert-butylimido compounds of manganese-(VII) and -(VI)
  作者：Andreas A. Danopoulos、Geoffrey Wilkinson、Tracy K. N. Sweet、Michael B. Hursthouse

  DOI：10.1039/dt9940001037

  日期：——

  salts of the cation [Mn(NBut)3(NH2But)]+, with Li(NHBut) under selected conditions gave the paramagnetic manganese(VI) analogues of the manganate(VI) anion, [LiL]2[Mn(NBut)4][L = 1,2-dimethoxyethane (dme) or N,N,N′,N′-tetramethylethylenediamine (tmen)], and with HCl gave Mn(NBut)2(NHBut)Cl2, the reaction being reversed by addition of pyridine. Unstable compounds, e.g Mn(NBut)3(C6F5) and Mn(NBut)3(NHBut)

  乙腈中氯化锰（III）与NHR（SiMe 3）（R = Bu t或CMe 2 CH 2 Me）的相互作用产生了锰（VII）物种Mn（NR）3 Cl，为热稳定和空气稳定的绿色晶体。Mn（NBu t）3 Cl 1中的氯原子已被Br，OC（O）R（R = Me或CF 3）取代。OC 6 X 5（X = F或Cl），OCH（CF 3）2' SC 6 ˚F 5' Ç 6 ˚F 5或NHBu吨通过使用SiMe 3 Br和其他试剂的银，th或锂盐。化合物1与Ag（O 3 SCF 3）或AgPF 6和NH 2 Bu t的相互作用产生了阳离子[Mn（NBu t）3（NH 2 Bu t）] +的盐，并与Li（NHBu t）处于选择状态。条件给出了锰酸根（VI）阴离子的顺磁性锰（VI）类似物[LiL] 2 [Mn（NBu t）4 ] [L = 1,2-二甲氧基乙烷（dme）或N，N，N '，N'-四甲基乙二胺（
• 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
• Anionic and cationic Bi- and tri-nuclear tert-butylimido complexes of manganese-(V) and -(VI)
  作者：Andreas A. Danopoulos、Geoffrey Wilkinson、Tracy K. N. Sweet、Michael B. Hursthouse

  DOI：10.1039/dt9950000937

  日期：——

  [Mn(NBut)2(µ-NBut)]21 with lithium powder in 1,2-dimethoxyethane (dme) to give [Li(dme)]2[Mn(NBut)2(µ-NBut)}2]2, or with sodium amalgam in tetrahydrofuran (thf) to give [Na(thf)][Mn(NBut)2(µ-NBut)}2]3 which have oxidation states V,V and V,VI respectively. Interaction of 1 with iodine gave a mixed-valence (VI,V,VI) compound, [Mn(NBut)2(µ-NBut)2}2Mn]I34. Interaction of 3 with HgCl2 gave [Mn(NBut)2(µ-N

  通过在1,2-二甲氧基乙烷（dme）中用锂粉还原MnCl（NBu t）3或[Mn（NBu t）2（µ-NBu t）] 2 1来获得二聚阴离子配合物，得到[Li（dme） ）] 2 [Mn（NBu t）2（µ-NBu t）} 2 ] 2，或在四氢呋喃（thf）中与钠汞齐一起提供[Na（thf）] [Mn（NBu t）2（µ- NBu t）} 2 ] 3分别具有氧化态V，V和V，VI。互动1用碘给了一个混合价（VI，V，VI）化合物，[锰（NBU吨）2（μ-NBU吨）2 } 2 Mn]为我3 4。3与HgCl 2的相互作用得到[Mn（NBu t）2（µ-NBu t）2 } 2 Mn] 2 [Hg 2 Cl 6 ]·2CHCl 3 5a和[（Bu t N）2 Mn（µ-NBu t）2 Mn（NHBu t）（NBu t）] 2[Hg 3 Cl 8 ] 5b。三氟甲磺酸银氧化1会在CH 2 Cl
• WEAKLY COORDINATING ANIONS CONTAINING POLYFLUOROALKOXIDE LIGANDS
  申请人：COLORADO STATE UNIVERSITY RESEARCH FOUNDATION

  公开号：EP1025110B1

  公开（公告）日：2004-12-22
• 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.