K(1,2,4-tris(trimethylsilyl)cyclopentadienyl) | 103731-91-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: K(1,2,4-tris(trimethylsilyl)cyclopentadienyl)
• 英文别名: [η⁵-1,2,4-(Me₃Si)₃C₅H₂]K；potassium 1,2,4-tris(trimethylsilyl)cyclopentadienide；K[η5-C5H2(SiMe3)3-1,2,4]；K(Cp''')；potassium;[2,4-bis(trimethylsilyl)cyclopenta-1,3-dien-1-yl]-trimethylsilane
• CAS: 103731-91-5
• 化学式: C₁₄H₂₉Si₃*K
• 分子量: 320.739
• InChiKey: PLVKYHNYTVMEDN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.05
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  K(1,2,4-tris(trimethylsilyl)cyclopentadienyl) 在 strontium(II) iodide 作用下， 以 乙醚 为溶剂， 以40%的产率得到
  参考文献：
  名称：

  A Homologous Series of Base‐Free Organo(alkaline‐earth) Metallocenes: Synthesis and Molecular Structures of [1,2,4‐(SiMe ₃ ) ₃ C ₅ H ₂ ] ₂ (Ca, Sr, Ba)

  摘要：

  AbstractBis[1,2,4‐tris(trimethylsilyl)cyclopentadienyl] complexes [1,2,4‐(SiMe3)3C5H2]2Ae [(Cp3Si)2Ae; Ae = Ca (1), Sr (2), Ba (3)] are isolated from the 2:1 reaction of K[Cp3Si] and AeI2 in diethyl ether. Under the same reaction conditions used for the heavier metallocenes, the corresponding (Cp3Si)2Be compound was not formed, although calculations suggest that the beryllocene would be sterically feasible. Compound 1 crystallizes as a bent monomer from hexanes (ring centroid−Ca−ring centroid = 166.7°) with two η5‐Cp3Si ligands on the calcium atom [Ca−C(av) = 2.63(2) Å]. Metallocene 2, the first crystallographically characterized example of an unsolvated strontocene, is also isolated as a bent monomer (159.4°) from hexanes with two η5‐Cp3Si ligands on the strontium atom [Sr−C(av) = 2.819(2) Å]. Compound 3 crystallizes on sublimation as a coordination dimer in which each barium atom is flanked by two η5‐Cp3Si rings [Ba−C(av) = 3.01(2) Å] and one methyl group from a neighboring Cp′ ring; the intermolecular Ba···C(methyl)′ distance is 3.275(6) Å. The amount of bending observed in 1−3 and other Group‐2 metallocenes varies with the metals, the steric bulk of the cyclopentadienyl ligands, and crystal packing effects, and is not easily predictable. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejic.200300284

文献信息

• SmCp^R₂-mediated cross-coupling of allyl and propargyl ethers with ketoesters and a telescoped approach to complex cycloheptanols
  作者：Mateusz P. Plesniak、Xavier Just-Baringo、Fabrizio Ortu、David P. Mills、David J. Procter

  DOI：10.1039/c6cc07318b

  日期：——

  A highly regio- and diastereoselective cross-coupling of allyl/propargyl ethers and [small beta]-ketoesters, mediated by SmCpR2 reagents, delivers decorated [small delta]-lactones. Screening of the Cp ligands on Sm(II) was employed to achieve high...

  由SmCpR2试剂介导的烯丙基/炔丙基醚与小β-酮酸酯的高度区域选择性和非对映选择性交叉偶联可产生修饰的小δ-内酯。通过筛选Sm（II）上的Cp配体来实现高...
• A structural investigation of heteroleptic lanthanide substituted cyclopentadienyl complexes
  作者：Fabrizio Ortu、Jonathan M. Fowler、Matthew Burton、Alasdair Formanuik、David P. Mills

  DOI：10.1039/c5nj00761e

  日期：——

  The synthesis and structural authentication of novel heteroleptic lanthanide complexes supported by bulky cyclopentadienyl ligands is herein presented. Steric effects play a fundamental role in the coordination motifs.

  这里介绍了由庞大环戊二烯基配体支持的新型杂叶系锗配合物的合成和结构鉴定。立体效应在配位基团中起着基本作用。
• Synthesis and structural characterization of lanthanum and cerium substituted cyclopentadienyl borohydride complexes
  作者：Fabrizio Ortu、Daniel Packer、Jingjing Liu、Matthew Burton、Alasdair Formanuik、David P. Mills

  DOI：10.1016/j.jorganchem.2017.09.010

  日期：2018.2

  borohydrides [Ln(BH4)3(THF)n] [Ln = La, n = 4 (1); Ln = Ce, n = 3.5] were treated with the substituted cyclopentadienyl potassium transfer agents KCptt (Cptt = C5H3tBu2-1,3), KCpttt (Cpttt = C5H2tBu3-1,2,4) and KCp′′′ (Cp′′′ = C5H2(SiMe3)3-1,2,4) in various reaction conditions to yield the heteroleptic lanthanide complexes [La(Cptt)2(μ-BH4)]2 (2), [La(Cpttt)(BH4)2(THF)2] (3), [La(Cpttt)(μ-BH4)2]6 (4), [Ce

  镧系元素硼氢化物[Ln（BH 4）3（THF）n ] [Ln = La，n = 4（1）; Ln为铈，N = 3.5]用取代的环戊二烯钾转移剂KCP处理TT（CP TT  = C 5 H ^ 3吨卜2 -1,3），KCP TTT（CP TTT  = C 5 H ^ 2吨卜3 - 1,2,4）和KCP'''（CP '''  = C 5 H 2（SiMe 3）3-1,2,4-）在各种反应条件，得到杂镧系络合物[拉（CP TT）2（μ-BH 4）] 2（2），[拉（CP TTT）（BH 4）2（THF）2 ]（3），[拉（CP TTT）（μ-BH 4）2 ] 6（4），[CE（CP TTT）（BH 4）（μ-BH 4）（THF）] 2（5）， [La（CP TTt）2（BH 4）]（6）和[Ln（CP）2（BH 4）（THF）]（Ln = La，7 ; Ce，8）通过盐复分解方案进行。配合物1–
• Synthesis of heteroleptic yttrium and dysprosium 1,2,4-tris(trimethylsilyl)cyclopentadienyl complexes
  作者：Sophie C. Corner、Conrad A. P. Goodwin、Fabrizio Ortu、Peter Evans、Hongrui Zhang、Gemma K. Gransbury、George F. S. Whitehead、David P. Mills

  DOI：10.1071/ch21314

  日期：——

  We report the synthesis of heteroleptic dysprosium complexes of the 1,2,4-tris(trimethylsilyl)cyclopentadienyl ligand (Cp‴=C5H2(SiMe3)3-1,2,4}), and diamagnetic yttrium analogues, by salt metathesis protocols from KCp‴ and molecular lanthanoid halide or borohydride precursors: [Ln(Cp‴)2(μ-Cl)2K}2]∞ (1-Ln; Ln = Y, Dy), [Ln(Cp‴)2(THF)(Cl)] (2-Ln; Ln = Y, Dy), [Y(Cp‴)2(η3-C3H5)] (3-Y), [Y(Cp‴)(BH4)2(THF)] (4-Y), [Dy(Cp‴)(BH4)(μ-BH4)]4 (5-Dy) and [Ln(Cp‴)2(BH4)] (6-Ln; Ln = Y, Dy); several crystals of [Dy(Cp‴)2(BH4)(THF)] (7-Dy) formed on one occasion during the isolation of 6-Dy. Efforts to prepare the isolated lanthanoid metallocenium cations [Ln(Cp‴)2]+ for Y and Dy were not successful by the anion abstraction methods investigated herein; however, several crystals of the contact ion-pair complex [Y(Cp‴)2(μ-Ph)2BPh2}] (8-Y) formed from the reaction of 3-Y with [NEt3H][BPh4]. On one occasion during the preparation of 3-Y we isolated several crystals of [Mg(Cp‴)(THF)(μ-Cl)]2. Complexes 1–6 and [NEt3H][BPh4] were all structurally authenticated by single crystal XRD and characterised by IR spectroscopy and elemental analysis, with magnetic susceptibility for dysprosium complexes determined by the Evans method, and yttrium analogues studied by multinuclear NMR spectroscopy; complexes 7-Dy, 8-Y, and [Mg(Cp‴)(THF)(μ-Cl)]2 were characterised by single crystal XRD only. The magnetic properties of 5-Dy were probed by SQUID magnetometry and ab initio calculations.

  我们报告了 1,2,4-三(三甲基硅烷基)环戊二烯配体（Cp‴=C5H2(SiMe3)3-1,2,4}）的异极性镝配合物和二磁性钇类似物的合成过程，这些配合物是通过 KCp‴和分子镧卤化物或硼氢化物前体的盐代合成协议合成的：Ln(Cp‴)2(μ-Cl)2K}2]∞（1-Ln；Ln = Y、Dy）、[Ln(Cp‴)2(THF)(Cl)]（2-Ln；Ln = Y、Dy）、[Y(Cp‴)2(η3-C3H5)]（3-Y）、[Y(Cp‴)(BH4)2(THF)]（4-Y）、[Dy(Cp‴)( )(μ- )]4（5-Dy）和[Ln(Cp‴)2( )]（6-Ln；Ln = Y、Dy）；在分离 6-Dy 的过程中，有一次形成了几种 [Dy(Cp‴)2( )(THF)]（7-Dy）晶体。本文所研究的阴离子抽取方法未能成功制备出 Y 和 Dy 的分离镧系金属硒阳离子 [Ln(Cp‴)2]+；不过，3-Y 与 [NEt3H][BPh4] 反应形成了几种接触离子对配合物 [Y(Cp‴)2(μ-Ph)2BPh2}] (8-Y) 的晶体。在制备 3-Y 的过程中，我们曾分离出几块 [Mg(Cp‴)(THF)(μ-Cl)]2 晶体。络合物 1-6 和 [NEt3H][BPh4] 均通过单晶 XRD 进行结构鉴定，并通过红外光谱和元素分析进行表征，镝络合物的磁感应强度通过埃文斯法测定，钇类似物则通过多核核磁共振光谱进行研究；络合物 7-Dy、8-Y 和 [Mg(Cp‴)(THF)(μ-Cl)]2 仅通过单晶 XRD 进行表征。5-Dy 的磁性能是通过 SQUID 磁力计和 ab initio 计算探测的。
• Mono-cyclopentadienyl complexes of lanthanum: synthesis and characterization of anilido derivatives
  作者：Garth R. Giesbrecht、Gavin E. Collis、John C. Gordon、David L. Clark、Brian L. Scott、Ned J. Hardman

  DOI：10.1016/j.jorganchem.2004.03.042

  日期：2004.7

  THF/pyridine to form the mono-ring complex (Cp‴)LaI2(py)3 (1) (py=pyridine); a minor product of this reaction is the bis-ring species (Cp‴)2LaI(py) (2). The solid state structure of 2 reveals a monomeric compound containing a pseudo-tetrahedral metal center exhibiting no unusual intramolecular contacts. Addition of one equiv of KNHAr (Ar=2,6-iPr2C6H3) to complex 1 in THF generates the mono-anilido compound

  笨重的配位体的环戊二烯基的使用[η 5 -C 5 H ^ 2（森达3）3 -1,2,4-] -（CP'''）允许对单体的分离，单环镧系元素的种类。如先前报道，（CP‴）K与LAI 3（THF）4（THF =四氢呋喃）在THF /吡啶中反应形成单环络合物（CP‴）LAI 2（py）3（1）（py =吡啶）; 此反应的次要产物是双环物种（CP ‴ ）2 LAI（py）（2）。的固态结构2揭示了一种单体化合物，该化合物含有不表现出异常分子内接触的拟四面体金属中心。在THF中向配合物1中添加一当量的KNHAr（Ar = 2,6- i Pr 2 C 6 H 3）生成单苯胺基化合物（CP‴）LAI（NHAr）（THF）2（3）被转化成更稳定的加合物的吡啶（CP'''）LAI（NHAr）（PY）2（4）通过添加吡啶至3。X射线晶体结构为3表示三角双锥体金属中心，带苯胺基基团的反式碘原子（N1-LA1-I1