tris(pentamethylcyclopentadienyl)lanthanum | 385828-44-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: tris(pentamethylcyclopentadienyl)lanthanum
• 英文别名: tris(pentamethylcyclopentadienyl)lanthanum(III)；lanthanum tris(pentamethylcyclopentadienyl)；[(C5Me5)3La]；(pentamethylcyclopentadienyl)3La；(η5-C5Me5)3La；La(η5-C5Me5)3；lanthanum(3+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene
• CAS: 385828-44-4
• 化学式: C₃₀H₄₅La
• 分子量: 544.593
• InChiKey: WXNXEEICXKSSHR-UHFFFAOYSA-N

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：

  tris(pentamethylcyclopentadienyl)lanthanum 、 双(三甲基硅烷基)氨基钾 以 苯 为溶剂， 以99%的产率得到Cp2*LaN(SiMe3)2
  参考文献：
  名称：

  (C5Me5)3LaLx 复合物的反应性：合成具有两个附加配体 (C5Me5)3La(NCCMe3)2 的三（五甲基环戊二烯基）复合物

  摘要：

  三（五甲基环戊二烯基）复合物中空间拥挤的限制已通过分离具有此配体集的第一个化合物和两个额外的配体 (C(5)Me(5))(3)ML(2) 得到扩展。这一结果是在研究添加的配体对空间拥挤 (C(5)Me(5))(3)La, 1 反应性的影响时获得的。 尽管 THF 和 Ph(3)PO 均未形成可结晶表征的 (C (5)Me(5))(3)LaL(x) 与 1 复合，这些 (C(5)Me(5))(3)La/L(x) 混合物与 1 相比显示出增强的反应性与底物如C(8)H(8) 和 CO(2)。使用金刚烷基叠氮化物 AdN(3) 制备 (C(5)Me(5))(3)LaL(x) 复合物的尝试导致了第一个叠氮化物插入金属环戊二烯键以生成 (C(5) )Me(5))(2)La[eta(2)-(N,N')-(C(5)Me(5))NN'N''Ad](N(3)Ad)。

  DOI：

  10.1021/ja808763y
• 作为产物：
  描述：

  tris(η5-pentamethylcyclopentadienyl)neodymium(III) 、 [(C5Me5)2La][(μ-Ph)2BPh2] 以 氘代苯 为溶剂， 生成 [(η5-pentamethylcyclopentadienyl)2Nd(μ-Ph)2BPh2] 、 tris(pentamethylcyclopentadienyl)lanthanum
  参考文献：
  名称：

  Defining Reactivity Differences in Sterically Crowded (η⁵-C₅Me₅)₃M Complexes Based on Metal Size and Lanthanide vs Actinide Effects

  摘要：

  Reactions between (eta(5)-C5Me5)(3)M and (eta(5)-O5Me5)(2)M'(mu-Ph)(2)BPh2 (M, M' = La, Ce, Pr, Nd, Sm, and U; M radius < M' radius) were examined to evaluate the relative steric crowding in the (C5Me5)(3)M series as a function of metal size and 4f vs 5f electron configuration. The sterically more crowded (C5Me5)(3)M complexes transfer (C5Me5)(-) to (C5Me5)(2)M'(mu-Ph)(2)BPh2 to generate less crowded (C5Me5)(3)M' products and (C5Me5)(2)M(mu-Ph)(2)BPh2 in mixtures with equilibrium constants in the range that allows all four components to be observed by NMR spectroscopy. The (C5Me5)(3)M to (C5Me5)(3)M' ratios depend on the difference in size of the two metals. Hence, (C5Me5)(3)Sm and (C5Me5)(2)La(mu-Ph)(2)BPh2 form a mixture with 99% (C5Me5)(3)La and 1% (C5Me5)(3)Sm, but the analogous reaction with (C5Me5)(2)Nd(mu-Ph)(2)BPh2 contains 90% (C5Me5)(3)Nd and 10% (C5Me5)(3)Sm. In analogous reactions with (C5Me5)(2)U(mu-Ph)(2)BPh2 and (C5Me5)(3)Ln lanthanide complexes, a size dependence is also observed, but the (C5Me5)3Ln complexes are favored over (C5Me5)(3)U to a greater extent than expected based on size differences.

  DOI：

  10.1021/om101149z

文献信息

• Synthesis and Comparative η¹-Alkyl and Sterically Induced Reduction Reactivity of (C₅Me₅)₃Ln Complexes of La, Ce, Pr, Nd, and Sm
  作者：William J. Evans、Jeremy M. Perotti、Stosh A. Kozimor、Timothy M. Champagne、Benjamin L. Davis、Gregory W. Nyce、Cy H. Fujimoto、Robert D. Clark、Matthew A. Johnston、Joseph W. Ziller

  DOI：10.1021/om050402l

  日期：2005.8.1

  previously described Ce or Pr complexes containing the (C5Me5)- ligand. The η1-C5Me5 alkyl-like reactivity of the (C5Me5)3Ln complexes was investigated with CO, ethylene, THF, and H2. The sterically induced reduction (SIR) reactivity of the (C5Me5)3Ln complexes was examined with SePPh3, AgBPh4, C8H8, and phenazine. All of these data indicate that (C5Me5)3Ln reactivity increases with decreasing size

  的合成（C 5我5）3 Ce和（C 5我5）3镨从[（C 5我5）2 LN] [（μ-PH）2 BPH 2 ]和KC 5我5完成该系列的较大的镧系元素La-Nd和Sm在空间上拥挤（C 5 Me 5）3 Ln络合物，并且可以比较结构和反应性随金属尺寸的变化。这些新的（C 5 Me 5）3的合成Ln配合物需要甲硅烷基化的玻璃器皿，这在空间上更拥挤的类似物上是不必要的。（C 5 Me 5）3 Ce和（C 5 Me 5）3 Pr显示比任何先前描述的包含（C 5 Me 5）-配体的Ce或Pr配合物更长的Ln-C（C 5 Me 5）距离。在η 1 -C 5我5烷基，如（C反应性5我5）3成LN络合物用CO，乙烯，THF，和H调查2。用Se PPh 3，AgBPh 4，C 8 H 8和吩嗪检查（C 5 Me 5）3 Ln复合物的空间诱导还原（SIR）反应性。所有这些数据表明，（C 5 Me 5）3 Ln
• Cyclopentadienyl ring metathesis with bis(pentamethylcyclopentadienyl)calcium as a route to mixed ring organolanthanide complexes; the crystal structure of (C5Me5)2Nd(C5H5)
  作者：Pamela S. Tanner、David J. Burkey、Timothy P. Hanusa

  DOI：10.1016/0277-5387(94)00316-7

  日期：1995.1

  Bis(pentamethylcyclopentadienyl)calcium, (C5Me5)2Ca, can be made by the reaction of Ca[N(SiMe3)2]2 with C5Me5H in toluene. It undergoes cyclopentadienyl ring metathesis with tris(cyclopentadienyl)lanthanide complexes, Cp3Ln (Ln = La, Nd, Sm) in toluene to generate the mixed ring complexes (C5Me5)2LnCp. The X-ray crystal structure of (C5Me5)2NdCp shows that the complex is a sterically crowded monomer

  双（五甲基环戊二烯基）钙（C 5 Me 5）2 Ca可以通过Ca [N（SiMe 3）2 ] 2与C 5 Me 5 H在甲苯中的反应制得。它与三（环戊二烯基）镧系元素络合物CP 3 Ln（Ln = La，Nd，Sm）在甲苯中进行环戊二烯基环复分解反应，生成混合环络合物（C 5 Me 5）2 LnCP。的（C的X射线晶体结构5我5）2 NDCP表明该复合物是一个在空间上拥挤的单体η 5 -C5 Me 5和CP环。C 5 Me 5和CP环的平均NdC距离为2.76–2.79Å。
• Sigma bond metathesis with pentamethylcyclopentadienyl ligands in sterically crowded (C5Me5)3M complexes
  作者：Thomas J. Mueller、Joseph W. Ziller、William J. Evans

  DOI：10.1039/c002654a

  日期：——

  reactions with (C5Me5)3Ce and (C5Me5)3U gave a mixture of C5Me5SPh and (C5Me5)2 as byproducts. PhSSPh reactions with the lanthanide nitrile adducts, (C5Me5)3Ln(NCCMe3)2 (Ln = La, Ce) and (C5Me5)3Nd(NCCMe3), formed [(C5Me5)2Ln(SPh)(NCCMe3)]2 and only C5Me5SPh as the byproduct. PhSeSePh reactions paralleled the PhSSPh results, but reactions of PhTeTePh with (C5Me5)3La, (C5Me5)3Sm, and (C5Me5)3La(NCCMe3)2

  为了进一步探索（C 5 Me 5）-配体在空间拥挤的（C 5 Me 5）3 M配合物中的反应性，与博士 （E = S， 硒， 特）已检查。与M =啦啦， 镨， 钕， m， 和 ÿ， 物理化学反应形成预期的还原产物[（C 5 Me 5）2 M（SPh）] 2，但主要的有机副产物不是空间诱导的还原产物（C 5 Me 5）2。相反，sigma键易位产物C 5 Me 5 SPh是主要的副产物。相反，与（C 5 Me 5）3 Ce和（C 5 Me 5）3 U的反应得到C 5 Me 5 SPh和（C 5 Me 5）2的混合物 作为副产品。 物理化学与镧系元素腈加合物（C 5 Me 5）3 Ln（NCCMe 3）2（Ln =啦啦， 铈）和（C 5 Me 5）3 Nd（NCCMe 3），形成[（C 5 Me 5）2 Ln（SPh）（NCCMe 3）] 2，仅形成C 5 Me 5 SPh作为副产物。硒化硒 反应与PhSSPh结果平行，但
• Trivalent [(C₅Me₅)₂(THF)Ln]₂(μ<i>-</i>η<i>²</i>:η<i>²</i>-N₂) Complexes as Reducing Agents Including the Reductive Homologation of CO to a Ketene Carboxylate, (μ-η⁴-O₂CCCO)²^-
  作者：William J. Evans、David S. Lee、Joseph W. Ziller、Nikolas Kaltsoyannis

  DOI：10.1021/ja0640851

  日期：2006.11.1

  KC(8), and N(2). Complex 1 reduces phenazine, cyclooctatetraene, anthracene, and azobenzene to form [(C(5)Me(5))(2)La](2)[mu-eta(3):eta(3)-(C(12)H(8)N(2))], 2, (C(5)Me(5))La(C(8)H(8)), 3, [(C(5)Me(5))(2)La](2)[mu-eta(3):eta(3)-(C(14)H(10))], 4, and [(C(5)Me(5))La(mu-eta(2)-(PhNNPh)(THF)](2), 5, respectively. Neither stilbene nor naphthalene are reduced by 1, but 1 reduces CO to make the ketene carboxylate

  [Z(2)Ln(THF)](2)(mu-eta(2)():eta(2)()-N(2)) 配合物（Z = 单阴离子配体）通过用三价二氮还原生成镧系元素盐和碱金属本身就是强还原剂，为还原性镧系元素化学提供了另一种选择。因此，可以使用二氮还原产物 [(C(5)Me(5))(2)(THF)La](2)(mu-eta(2) ():eta(2)()-N(2)), 1, 很容易从 [(C(5)Me(5))(2)La][BPh(4)], KC(8) 和N(2)。配合物 1 还原吩嗪、环辛四烯、蒽和偶氮苯，形成 [(C(5)Me(5))(2)La](2)[mu-eta(3):eta(3)-(C(12) H(8)N(2))], 2, (C(5)Me(5))La(C(8)H(8)), 3, [(C(5)Me(5))(2 )La](2)[mu-eta(3):eta(3)-(C(14)H(10))], 4, and
• Reductive Reactivity of the Organolanthanide Hydrides, [(C₅Me₅)₂LnH]_<i>x</i>, Leads to <i>ansa</i>-Allyl Cyclopentadienyl (η⁵-C₅Me₄CH₂−C₅Me₄CH₂-η³)^2- and Trianionic Cyclooctatetraenyl (C₈H₇)^3- Ligands
  作者：William J. Evans、Benjamin M. Schmiege、Sara E. Lorenz、Kevin A. Miller、Timothy M. Champagne、Joseph W. Ziller、Antonio G. DiPasquale、Arnold L. Rheingold

  DOI：10.1021/ja8011726

  日期：2008.7.1

  3)-C10H14), respectively, but the analogous [(C5Me5)2LaH]x and [(C5Me5)2YH]2 reactions are more complicated. All three lanthanide hydrides reduce C8H8 to make (C5Me5)Ln(C8H8) and (C5Me5)3Ln, a reaction that constitutes another synthetic route to (C5Me5)3Ln complexes. In the reaction of [(C5Me5)2YH]2 with C8H8, two unusual byproducts are obtained. In benzene, a (C5Me5)Y[(eta(5)-C5Me4CH2-C5Me4CH2-eta(3))]

  检查 [(C5Me5)2LnH]x 配合物 (Ln = Sm, La, Y) 中镧系元素氢化物配体的还原反应性，以查看这些氢化物配体是否会像 [(C5Me5)2AnH2]2 中的锕系氢化物那样反应 (An = U, Th) 和 [(C5Me5)2UH]2。每个镧系元素氢化物复合物都以大约 90% 的产率还原 PhSSPh 以制备 [(C5Me5)2Ln(mu-SPh)]2。[(C5Me5)2SmH]2 还原吩嗪和蒽，生成 [(C5Me5)2Sm]2(mu-eta(3):eta(3)-C12H8N2) 和 [(C5Me5)2Sm]2(mu-eta(3) :eta(3)-C10H14)，但类似的 [(C5Me5)2LaH]x 和 [(C5Me5)2YH]2 反应更复杂。所有三种镧系元素氢化物都将 C8H8 还原成 (C5Me5)Ln( ) 和 (C5Me5)3Ln，这一反应构成了 (C5Me5)3Ln