bis(η5-1,3-bis(trimethylsilyl)cyclopentadienyl)yttrium iodide | 1352966-49-4

• 英文名称: bis(η5-1,3-bis(trimethylsilyl)cyclopentadienyl)yttrium iodide
• 英文别名: C₅H₄SiMe₃；[(C₅H₃(SiMe₃)₂)₂YI]
• CAS: 1352966-49-4
• 化学式: C₂₂H₄₂ISi₄Y
• 分子量: 634.728
• InChiKey: DUQSGOBUGBXAGR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  bis(η5-1,3-bis(trimethylsilyl)cyclopentadienyl)yttrium iodide 、 sodium methylcyclopentadienide 以 甲苯 为溶剂， 生成 [(C₅H₃(SiMe₃)₂)₂Y(C₅H₄Me)] 、 [(C₅H₃(SiMe₃)₂)Y(C₅H₄Me)₂]
  参考文献：
  名称：

  通过还原三（环戊二烯基）前体，包括茚基阴离子的C–H键活化，来合成Ln2 +配合物的配体效应

  摘要：

  The tris(cydopentadienyl) yttrium complexes Cp3Y(THF), (Cp3Y)-Y-Me(THF), Cp-3 '' Y, Cp-2 '' YCp, and Cp-2 '' YCpMe [Cp = C5H5, Cp-Me = C5H4Me, Cp '' = C5H3(SiMe3)(2)] have been treated with potassium graphite in the presence of 2.2.2-cryptand to search for more stable examples of complexes featuring the recently discovered Y2+ ion first isolated in [K(18-crown-6)][Cp-3'Y] and [K(2.2.2-cryptand)][Cp-3'Y], 1-Y (Cp' = C5H4SiMe3). Reduction of the tris(cyclopentadienyl) complexes generates dark solutions like that of 1-Y, and the EPR spectra contain doublets with g values between 1.990 and 1.991 and hyperfine coupling constants of 34-47 gauss that are consistent with the presence of Y2+. [K(2.2.2-cryptand)][Cp-2 '' YCp], 2-Y, was characterizable by X-ray crystallography. Reduction of the Cp-3 '' Gd, Cp-2 '' GdCp, and Cp-2 '' GdCpMe complexes containing the larger metal gadolinium were also examined. In each case, dark solutions and EPR spectra like that of [K(2.2.2-cryptand)][Cp-3'Gd], 1-Gd, were obtained, and [K(2.2.2-cryptand)][Cp-2 '' GdCp], 2-Gd, was crystallographically characterizable. None of the new yttrium and gadolinium complexes displayed greater stability than 1-Y and 1-Gd. Exploration of this reduction chemistry with indenyl ligands did not give evidence for +2 complexes. The only definitive information obtained from reductions of the Cp(3)(In)Ln (Cp-In = C9H7, Ln = Y, Ho, Dy) complexes was the X-ray crystal structure of {K(2.2.2-cryptand)}(2){[(C9H7)(2)Dy(mu-eta(5):eta(1)-C9H6)](2)}, a complex containing the first example of the indenyl dianion, (C9H6)(2-), derived from C-H bond activation of the (C9H7)(1-) monoanion. Density functional theory analysis of these results provides an explanation for the observed hyperfine coupling constants in the yttrium complexes and for the C-H bond activation observed for the indenyl complex.

  DOI：

  10.1021/acs.organomet.5b00500
• 作为产物：
  描述：

  [YI₃(THF)_3.5] 、 1,3-ditrimethylsilylcyclopentadienyl potassium 以 四氢呋喃 为溶剂， 以87%的产率得到bis(η5-1,3-bis(trimethylsilyl)cyclopentadienyl)yttrium iodide
  参考文献：
  名称：

  Syntheses and Structures of the Crystalline, Highly Crowded 1,3-Bis(trimethylsilyl)cyclopentadienyls [MCp″₃] (M = Y, Er, Yb), [PbCp″₂], [{YCp″₂(μ-OH)}₂], [(ScCp″₂)₂(μ-η²:η²-C₂H₄)], [YbCp″₂Cl(μ-Cl)K(18-crown-6)], and [{KCp″}_∞]

  摘要：

  Yttrium and the smaller group 3 and 4f metal homoleptic M(III) cyclopentadienyls [MCp ''(3)] (Cp '' = [eta(5)-C5H3(SiMe3)(2)-1,3](-) and M = Y (1Y), Er (1Er), or Yb (1Yb)) were prepared from YCp '' I-2 (2Y) or the appropriate [LnCp '' I-2(thf)] and KCp '' in satisfactory (1Y), very low (1Er), or low (1Yb) yield. Attempted reaction of [ScCp '' I-2(thf)] with KCp '' failed to produce the homoleptic Sc(III) cyclopentadienyl. Compound 1Yb was synthesized in better yield by the redox reaction between [YbCp ''(2)(thf)] and either [PbCp ''(2)] (3) or the in situ prepared HgCp ''(2) (4) analogue. Complexes 3 and 4 were obtained by a salt metathesis route, 3 was isolated as a crystalline solid, while 4 was used only as a hexane solution. The structures of crystalline 1Y, 1Yb, 3, [{YCp ''(2)(mu-OH)}(2)] (5Y) [prepared by hydrolysis of 1Y], [(ScCp ''(2))(2)-(mu-eta(2):eta(2)-C2H4)] (6) {isolated in low yield from the reaction of ScCp '' I-2 (2Sc) with [K(18-crown-6)](2)[C6H2(SiMe3)(4)-1,2,4,5]}, [LaCp '' Cl-2(mu-Cl)K(18-crown-6)] (7La) {obtained from the foregoing potassium reagent and [{LaCp ''(2)(mu-Cl)}(2)]}, [YbCp '' Cl-2(mu-Cl)K(18-crown-6)] (7Yb), and [{KCp ''}(infinity)] (8) were determined by X-ray diffraction.

  DOI：

  10.1021/om2009364