GdCl3(THF)4 | 148573-75-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: GdCl3(THF)4
• 英文别名: GdCl3(tetrahydrofuran)4；gadolinium(3+);oxolane;trichloride
• CAS: 148573-75-5
• 化学式: C₁₆H₃₂Cl₃GdO₄
• 分子量: 552.037
• InChiKey: KDAREYYHYJNJPH-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  5.26
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [N(2,6-dimethylphenyl)C(Me)]2CH2 、 GdCl3(THF)4 在 n-C₄H₉Li 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以87%的产率得到[GdCl2(THF)2(((2,6-C6H3Me2)NHC(Me)CHC(Me)N(2,6-C6H3Me2))]
  参考文献：
  名称：

  β-Diketiminato Rare-Earth Metal Complexes. Structures, Catalysis, and Active Species for Highly cis-1,4-Selective Polymerization of Isoprene

  摘要：

  Lithiation of the beta-diketimines (2,6-C6H3R2)NH=C(Me)CH=C(Me)N(2,6-C6H3R2) (R = Me (HL1), Et (HL2)) by nBuLi was followed by metathesis reaction with LnCl(3)(THF)(x) and Y(BH4)(3)(THF)(2) to afford the corresponding complexes L(1)LnCl(2)(THF)(2) (Ln = Gd (1), Nd (3), Dy (4), Er (5), Y (6)), (LGdCl2)-Gd-2(THF)2 (2), and (LY)-Y-1(BH4)(2)(THF) (8), respectively. Treatment of neutral HL1 with Y(CH2SiMe3)(3)(THF)(2) generated the bis(alkyl) complex 7, (LY)-Y-1(CH2SiMe3)(2)-(THF). Upon activation with [PhNHMe2][B(C6F5)(4)] and AliBu(3), complex 6 showed the highest cis1,4 selectivity (99.3%, T-p = 0 degrees C) toward the polymerization of isoprene, while complex 7 had a comparatively low cis-1,4 selectivity, and in contrast, complex 8 was completely inert. The influences of the ortho substituents of the N-aryl rings of the ligands, the types of central metals and cocatalysts, and addition sequence of the catalyst components had been thoroughly investigated. By means of X-ray diffraction and H-1 NMR spectroscopy analyses, the intermediates arising from the stoichiometric reactions among the catalyst components and the probable active species were elucidated, which facilitates further investigation of the mechanism for diene polymerization.

  DOI：

  10.1021/om100100r
• 作为产物：
  描述：

  四氢呋喃 、 gadolinium(III) chloride hexahydrate 在 SOCl₂ 作用下， 以 四氢呋喃 为溶剂， 以84.2%的产率得到GdCl3(THF)4
  参考文献：
  名称：

  氯化镧（III）-四氢呋喃溶剂化物：LnCl3（THF）n系列中的结构模式，其中n = 2,3,3.5和4：[PrCl（μ-Cl）2（THF）2] n的晶体和分子结构，[Nd（μ-Cl）3（H2O）（THF）] n和GdCl3（THF）4

  摘要：

  摘要制备了tetra（Ⅲ），钕（Ⅲ）和g（Ⅲ）与四氢呋喃（THF）的加合物，并通过X射线晶体学对其结构进行了表征。在过量THF存在下使用亚硫酰氯从相应的六水合物LnCl3（H2O）6去除水，得到[PrCl3（THF）2] n（1）的浅绿色立方晶体，[NdCl3（H2O）（ THF）] n（2）和GdCl3（THF）4（3）的无色针状晶体。在1中，每个m原子是7配位的，并通过双（μ-Cl）2卤素桥接单元与（两个）相邻的金属中心相连，从而形成聚合物链结构。金属几何形状近似为扭曲的五边形双锥体，其中PrClbridge2.852（6）–2.891（5），PrCl末端2.668（6），PrOTHF2.51（1）（轴向），2.53（2）A（赤道）。在图2中，该结构是二维交联聚合物，其中每个钕原子都通过双（μ-Cl）2卤素桥键与（三个）其他原子连接。每个金属中心的配位球均包含六个氯原子[NdClbridge2

  DOI：

  10.1016/s0277-5387(97)00078-8

文献信息

• Halide-abstraction reactions of tin(IV) and lanthanide(III) chlorides in tetrahydrofuran: crystal and molecular structures of [LnCl2(thf )5][SnCl5(thf  )] where Ln = Ce, Gd or Yb
  作者：Gerald R. Willey、Timothy J. Woodman、David J. Carpenter、William Errington

  DOI：10.1039/a702963b

  日期：——

  It has been established that halide abstraction from several lanthanide(III) chlorides can be effected by tin tetrachloride. Direct treatment (1∶1) of LnCl 3 where Ln = Ce, Gd or Yb with SnCl 4 in tetrahydrofuran (thf) provided colourless compounds of the generic type LnSnCl 7 (thf) 6 which have been identified by X-ray crystallography as ionic salts [trans-LnCl 2 (thf) 5 ][SnCl 5 (thf)]. The individual seven-co-ordinate cations feature a regular pentagonal-bipyramidal metal geometry in which a trans-LnCl 2 unit is surrounded by five thf molecules arranged in an equatorial plane. These co-ordinated solvent molecules adopt the familiar ‘propeller-like’ arrangement indicative of a skew as opposed to envelope ligand conformation. For Ln = Ce, Ce–Cl 2.697(2), Ce–O mean 2.495(5) Å; for Ln = Gd, Gd–Cl 2.608(2), Gd–O mean 2.415(4) Å; for Ln = Yb, Yb–Cl 2.5375(13), Yb–O mean 2.346(4) Å. The six-co-ordinate [SnCl 5 (thf)] - anions common to the series show a two-fold axis of symmetry containing the metal atom, the oxygen (thf) atom and a chloride atom mutually trans to the latter. Bond distances for Ln = Ce, i.e. Sn–O 2.276(7), Sn–Cl mean 2.399(2) Å, are typical for the series.

  已经证实，四氯化锡可以从几种镧系（III）氯化物中抽取卤化物。在四氢呋喃（thf）中用氯化锡 4 直接处理（1∶1）LnCl 3（其中 Ln = Ce、Gd 或 Yb），可得到无色的 LnSnCl 7 (thf) 6 通式化合物，经 X 射线晶体学鉴定为离子盐 [trans-LnCl 2 (thf) 5 ][SnCl 5 (thf)]。单个七配位阳离子具有规则的五角双锥金属几何形状，其中一个反式氯化锰 2 单元被排列在赤道面上的五个噻吩分子包围。这些配位溶剂分子采用了我们熟悉的 "螺旋桨式 "排列，表明配体的构象是倾斜的，而不是包络的。对于 Ln = Ce，Ce-Cl 2.697(2)，Ce-O 平均 2.495(5)埃；对于 Ln = Gd，Gd-Cl 2.608(2)，Gd-O 平均 2.415(4)埃；对于 Ln = Yb，Yb-Cl 2.5375(13)，Yb-O 平均 2.346(4)埃。该系列中常见的六配位[SnCl 5 (thf)] - 阴离子显示出包含金属原子、氧原子（thf）和与后者互为反式的氯原子的双重对称轴。Ln = Ce 的键距，即 Sn-O 2.276(7)埃，Sn-Cl 平均 2.399(2)埃，是该系列的典型键距。