(η3-allyl)bis(η5-pentamethylcyclopentadienyl)lanthanum(III) | 98720-50-4

• 英文名称: (η3-allyl)bis(η5-pentamethylcyclopentadienyl)lanthanum(III)
• 英文别名: (η(5)-C5Me5)2La(C3H5)；[(pentamethylcyclopentadienyl)2La(η3-allyl)]；(C5Me5)2La(η3-CH2CHCH2)
• CAS: 98720-50-4
• 化学式: C₂₃H₃₅La
• 分子量: 450.436
• InChiKey: NDHYDFGGZWDQDU-UHFFFAOYSA-N

计算性质

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

反应信息

• 作为反应物：
  描述：

  吡咯 、 (η3-allyl)bis(η5-pentamethylcyclopentadienyl)lanthanum(III) 以 甲苯 为溶剂， 以45 %的产率得到
  参考文献：
  名称：

  吡咯桥茂金属配合物：从合成、电子结构到单分子磁性

  摘要：

  吡咯基配体的π-和σ-碱性提供了多种配位模式。金属中心周围的空间阻碍配位球可能会促进吡咯基配体的新配位模式。在这里，我们提出了三种双核稀土配合物 [Cp* 2 RE(μ-pyr)] 2、[RE = Y ( 1 )、La ( 2 )、Dy ( 3 )；Cp*=五甲基环戊二烯基，pyr=吡咯基]，通过烯丙基配合物与H-吡咯之间的质子解反应合成。每种金属由两个 Cp* 配体和吡咯环的 N 原子连接，同时与另一个吡咯配体的 π 系统相互作用，产生前所未有的吡咯配位模式，最好描述为 [((η 5 -Cp * ) 2 RE) 2 (μ-1η 2 -pyr-2κN)(μ-2η 2 -pyr-1κN)]。Cp* 配体实现的空间拥挤迫使吡咯基配体的这种不对称配位。1 – 3通过晶体学、电化学和光谱学进行了表征。1 的密度泛函理论计算揭示了吡咯基配体与钇(III)离子之间的键合情况。令人兴奋的是，3在零直流场下表现出缓慢的磁弛豫，U

  DOI：

  10.1021/acs.inorgchem.3c01724
• 作为产物：
  描述：

  三聚丙烯 、 [(pentamethylcyclopentadienyl)2La(hydrido)]2 以 正戊烷 为溶剂， 生成 (η3-allyl)bis(η5-pentamethylcyclopentadienyl)lanthanum(III)
  参考文献：
  名称：

  Highly reactive organolanthanides. Systematic routes to and olefin chemistry of early and late bis(pentamethylcyclopentadienyl) 4f hydrocarbyl and hydride complexes

  摘要：

  DOI：

  10.1021/ja00312a050

文献信息

• Differentiating Chemically Similar Lewis Acid Sites in Heterobimetallic Complexes: The Rare-Earth Bridged Hydride (C₅Me₅)₂Ln(μ-H)₂Ln′(C₅Me₅)₂ and Tuckover Hydride (C₅Me₅)₂Ln(μ-H)(μ-η¹:η⁵-CH₂C₅Me₄)Ln′(C₅Me₅) Systems
  作者：Megan E. Fieser、Thomas J. Mueller、Jefferson E. Bates、Joseph W. Ziller、Filipp Furche、William J. Evans

  DOI：10.1021/om500624x

  日期：2014.7.28

  differentiating the chemistry of two closely related Lewis acidic metals in heterobimetallic complexes was addressed by studying hydrogenolysis and C–H bond activation reactions of bimetallic rare-earth hydride complexes. Hydrogenolysis of equimolar amounts of Cp*2Lu(η3-C3H5) (1-Lu) and Cp*2Y(η3-C3H5) (1-Y) (Cp* = C5Me5) forms a mixture of hydride complexes, the heterobimetallic compound Cp*2Lu(H)2YCp*2 (2-Lu/Y)

  通过研究双金属稀土氢化物配合物的氢解和CH键活化反应，解决了区分异双金属配合物中两种紧密相关的路易斯酸性金属的化学难题。的等摩尔量CP的氢解* 2路（η 3 -C 3 H ^ 5）（1-路）1和CP * 2 Y（η 3 -C 3 H ^ 5）（1-Y ）（CP * = C 5我5）形成氢化物络合物的混合物，杂双金属化合物CP * 2 Lu（H）2 YCP * 2（2-Lu / Y）和同双金属化合物（CP * 2 LuH）2（2-Lu / Lu）和（CP * 2 YH）2（2-Y / Y）。该混合物可以被分析和通过差异化1个H NMR光谱由于我= 1 / 2 89分别如图4所示，：Y核在约86的比率以显示这三种产品：10。加热该混合物导致C-H键活化和tuckover氢化物络合物的形成中，异核化合物的CP * 2 Y（μ-H）（μ-η 1：η 5 -CH 2 C ^ 5我4）LuCP *（3-Y
• 139La-NMR-spektroskopie an allyllanthan(III)-komplexen
  作者：H. Windisch、J. Scholz、R. Taube、B. Wrackmeyer

  DOI：10.1016/0022-328x(96)06259-6

  日期：1996.8

  La-139-NMR chemical shifts were measured for several anionic complexes of formulae [Li(C4H8O2)(3/2)][La(eta(3)-C3H5)(4)], [Li(C4H8O2)(2)][Cp(n)'La(eta(3)-C3H5)(4-n)](Cp' = Cp(eta(5)-C5H5); n = 1, 2 and Cp' = Cp*(eta(5)-C(5)Me(5)); n = 1) and Li[R(n)La(eta(3)-C3H5)(4-n)] (R = N(SiMe(3))(2); n = 1, 2 and R = C=CSiMe(3); n = 4), as well as for neutral compounds of formulae La(eta(3)-C3H5)(3)L(n) (L(n) = (C4H8O2)(1.5), (HMPT)(2), TMED), Cp(n)'La(eta(3)-C3H5)(3-n) (Cp' = Cp(eta(5)-C5H5), Cp*(eta(5)-C(5)Me(5)); n = 1, 2) and La(eta(3)-C3H5)(2)X(THF)(2) (X = Cl, Br, I). Typical ranges of the La-139-NMR chemical shifts were found for the different types of complex independent of number and kind of organyl groups directly bonded to lanthanum.
• Diazomethane Insertion into Lanthanide− and Yttrium−C(allyl) Bonds To Form the η²-Hydrazonato Complexes (C₅Me₅)₂Ln[η²(<i>N</i>,<i>N</i>′)-RNN═CHSiMe₃] (R = C₃H₅)
  作者：William J. Evans、Elizabeth Montalvo、Timothy M. Champagne、Joseph W. Ziller、Antonio G. DiPasquale、Arnold L. Rheingold

  DOI：10.1021/om800065j

  日期：2008.7.1

  (Trimethylsilyl)diazomethane, Me(3)SiCHN(2), is not metalated by the metallocene allyl complexes (C(5)Me(5))(2)Ln(C(3)H(5)) but instead inserts to form the lanthanide hydrazonato complexes (C(5)Me(5))(2)Ln)[eta(2)(N,N')- RNN=CHSiMe(3)] (R = CH(2)=CHCH(2); Ln = Sm, La, Y). Although the La, Y, and Sm complexes are isomorphous, the double bond in the allyl substituent is oriented toward La and away from Y and Sm.
• Facile Insertion of N₂O into Metal−Carbon Bonds of Metallocene Allyl Complexes to Form (RN₂O)⁻ Ligands
  作者：Selvan Demir、Elizabeth Montalvo、Joseph W. Ziller、Gerd Meyer、William J. Evans

  DOI：10.1021/om100917w

  日期：2010.12.13

  Attempts to generate a scandium metallocene oxide using N2O have revealed that N2O undergoes facile insertion into metal carbon bonds of allyl meiallocene complexes to form (RN2O)(-) ligands where R = C3H5. This has been demonstrated in reactions with the tetramethylcyclopentadienyl allyl complexes (C5Me4H)(2)M(eta(3)-C3H5)(M = Sc, Y) and the pentamethylcyclopentadienyl allyl compounds (C5Me5)(2)M(eta(3)-C3H5) (M = Y, Sm, La), which generate the insertion products [(C5Me4H)(2)M(mu-eta(1):eta(2)-ON=NC3H5)](2) (M = Sc, 1; Y, 2) and [(C5Me5)(2)M(mu-eta(1):eta(2)-ON=NC3H5)](2)(M = Y, 3; Sm, 4; La, 5), respectively.