[(C5Me4SiMe3)Lu(μ-H)(CH2SiMe3)(THF)]2 | 505028-70-6

• 英文名称: [(C5Me4SiMe3)Lu(μ-H)(CH2SiMe3)(THF)]2
• 英文别名: [C5Me4SiMe3Lu(CH2SiMe3)(μ-H)(THF)]2
• CAS: 505028-70-6
• 化学式: C₄₀H₈₂Lu₂O₂Si₄
• 分子量: 1057.37
• InChiKey: GKZNPFVKARHBLY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  [(C5Me4SiMe3)Lu(μ-H)(CH2SiMe3)(THF)]2 以 苯 为溶剂， 生成 [(η⁵-C₅Me₄(SiMe₃))Lu(CH₂SiMe₃)₂(thf)]
  参考文献：
  名称：

  Rare-Earth-Metal Mixed Hydride/Aryloxide Complexes Bearing Mono(cyclopentadienyl) Ligands. Synthesis, CO₂ Fixation, and Catalysis on Copolymerization of CO₂ with Cyclohexene Oxide

  摘要：

  Hydrogenolysis of mono(cyclopentadienyl)-ligated rare-earth-metal bis(alkyl) complexes Cp'Ln-(CH2SiMe3)2(THF) (Ln = Y (1a), Dy (1b), Lu (1c); Cp' = C5Me4SiMe3) with PhSiH3 afforded the mixed hydride/alkyl complexes [Cp'Ln(mu-H)(CH2SiMe3)(THF)](2) (Ln = Y (2a), Dy (2b), Lu (2c)). The overall structure of complexes 2a-c is a C-2-symmetric dimer containing a planar symmetric Ln(2)H(2) core at the center of the molecule. Deprotonation of ArOH (Ar = C6H2-Bu-t(2)-2,6-Me-4) by the metal alkyl group of 2a-c led to formation of the mixed hydride/aryloxide derivatives [Cp'Ln(mu-H)(OAr)](2) (Ln = Y (3a), Dy (3b), Lu (3c)), which adopt the dimeric structure through hydride bridges with trans-accommodated terminal aryloxide groups. Complexes 3a-c swiftly reacted with CO2 to generate the mixed formate/carbonate complexes [Cp'Ln(mu-eta(1):eta(1)-O2CH)(mu-eta(1):eta(1)-O2COAr)](2) (Ln = Y (4a), Dy (4b), Lu (4c)). The two Cp'Ln fragments in these complexes are bridged by the formate and carbonate species, respectively, to form two square-pyramidal geometries around the metal centers. Furthermore, complexes 3a-c initiated the copolymerization of CO2 and cyclohexene oxide (CHO) under mild conditions to afford polymers with modest molecular weights and high carbonate linkages (92-99%).

  DOI：

  10.1021/om800170x
• 作为产物：
  描述：

  [(η⁵-C₅Me₄(SiMe₃))Lu(CH₂SiMe₃)₂(thf)] 、 苯硅烷 以 正己烷 为溶剂， 以80%的产率得到[(C5Me4SiMe3)Lu(μ-H)(CH2SiMe3)(THF)]2
  参考文献：
  名称：

  Recent Progress in the Chemistry of Rare Earth Metal Alkyl and Hydrido Complexes Bearing Mono(cyclopentadienyl) Ligands

  摘要：

  稀土三（烷基）络合物与硅烷连接的环戊二烯-胺和-膦之间的酸碱反应可分别直接生成相应的环戊二烯-胺和-膦稀土烷基络合物。这种方法也可用于合成含有单（环戊二烯）配体（如 C5Me4SiMe3）的稀土双（烷基）络合物。烷基络合物与 H2 或 PhSiH3 反应后，很容易得到相应的氢化物络合物；在含有 C5Me4SiMe3 配体的双（烷基）络合物中，分离出了一种新型稀土多氢化物簇，并对其结构进行了表征。与硅烷基相连的环戊二烯-芳基酰胺和-膦基稀土烷基络合物分别是末端炔烃二聚化和烯烃氢硅化的极佳催化剂前体。稀土多氢簇对内酯、腈和烯烃等不饱和有机底物具有独特的反应活性。

  DOI：

  10.1246/bcsj.76.2253

文献信息

• Isolation and Structural Characterization of a Polyhydrido Lanthanide Cluster Complex Consisting of “(C₅Me₄SiMe₃)LuH₂” Units
  作者：Olivier Tardif、Masayoshi Nishiura、Zhaomin Hou

  DOI：10.1021/om021014b

  日期：2003.3.1

  Reaction of the mixed alkyl / hydride complex [Cp'Lu(CH2SiMe3)(mu-H)(THF)](2) (2; CP'= C3Me4SiMe3) with 1 equiv of PhSiH3 (per Lu) in benzene or OEt2 afforded the polyhydrido cluster [Cp'LuH2](4) (3), while hydrogenolysis of 2 with H-2 (1 atm) in THF yielded the THF-coordinated complex [Cp'Lu(mu-H)(2)](4)(THF) (4). Complexes 3 and 4 are interconvertible, without decomposition or ligand redistribution.