[(η⁵-C₅Me₄(SiMe₃))Lu(CH₂SiMe₃)₂(thf)] | 505028-69-3

• 英文名称: [(η⁵-C₅Me₄(SiMe₃))Lu(CH₂SiMe₃)₂(thf)]
• 英文别名: Cp′Lu(CH₂SiMe₃)₂(thf)；(η⁵-C₅Me₄(SiMe₃))′Lu(CH₂SiMe₃)₂(thf)；(C5Me4SiMe3)Lu(CH2SiMe3)2(THF)；[(η5-C5Me4SiMe3)Lu(THF)(CH2SiMe3)2]
• CAS: 505028-69-3
• 化学式: C₂₄H₅₁LuOSi₃
• 分子量: 614.892
• InChiKey: VOVRIYRWOGJWHN-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：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(η⁵-C₅Me₄(SiMe₃))Lu(CH₂SiMe₃)₂(thf)] 、 N,N'-di-p-tolylbenzamidine 以 甲苯 为溶剂， 反应 12.0h， 以78%的产率得到(η⁵-C₅Me₄(SiMe₃))'Lu{PhC(N(4-MeC₆H₄)₂)}₂
  参考文献：
  名称：

  像环戊二烯基一样的配体作为半三明治双（酰胺基）稀有金属配合物中的反应位点：胺在碳二亚胺催化加成反应中的有效应用

  摘要：

  一系列混合Cp的'/双（amidinato）（CP'=η 5 -C 5我4（森达3））镧系络合物通过1合成：Cp'Ln（CH 2之间的酸-碱反应2森达3）2（THF）（Ln为Y，镝，铒，Lu）和脒。这些CP'/双（amidinato）络合物显示出优异的催化活性的加成胺制碳二亚胺，得到相应的胍。双核酰胺配合物的分离，结构表征和催化应用清楚地表明，催化循环是由Cp'的解离引发的。这些结果表明，CP'，对于第一次，充当反应部位产生活性LN-N物种。

  DOI：

  10.1021/om5002793
• 作为产物：
  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

文献信息

• Recent Progress in the Chemistry of Rare Earth Metal Alkyl and Hydrido Complexes Bearing Mono(cyclopentadienyl) Ligands
  作者：Zhaomin Hou

  DOI：10.1246/bcsj.76.2253

  日期：2003.12

  The acid–base reactions between rare earth tris(alkyl) complexes and silylene-linked cyclopentadiene–amines and –phosphines afford straightforwardly the corresponding cyclopentadienyl–amido and –phosphido rare earth alkyl complexes, respectively. This method can also be utilized for the synthesis of rare earth bis(alkyl) complexes bearing mono(cyclopentadienyl) ligands such as C5Me4SiMe3. The reaction of the alkyl complexes with H2 or PhSiH3 readily gives the corresponding hydrido complexes; in the case of the bis(alkyl) complexes bearing the C5Me4SiMe3 ligand, a novel type of rare earth polyhydrido cluster has been isolated and structurally characterized. The silylene-linked cyclopentadienyl–arylamido and –phosphido rare earth alkyl complexes act as excellent catalyst precursors for the dimerization of terminal alkynes and hydrosilylation of olefins, respectively. The rare earth polyhydrido clusters exhibit unique reactivities toward unsaturated organic substrates such as lactones, nitriles, and olefins.

  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。
• Rare Earth/d-Transition Metal Heteromultimetallic Polyhydride Complexes Based on Half-Sandwich Rare Earth Moieties
  作者：Takanori Shima、Zhaomin Hou

  DOI：10.1021/om900024q

  日期：2009.4.13

  half-sandwich rare earth metal bis(alkyl) complexes Cp′Ln(CH2SiMe3)2(THF) (Cp′ = η5-C5Me4SiMe3; Ln = Y, Lu) with 1 equiv of the binuclear tungsten octahydride complex [Cp*WH4]2 (Cp* = η5-C5Me5) readily gave the corresponding Ln/W2 heterotrimetallic hexahydride complexes Cp′Ln(THF)(μ-H)6(WCp*)2 (Ln = Y (1a), Lu (1b)) with release of SiMe4. A similar reaction of (C5Me4R)Ln(CH2SiMe3)2(THF) with the binuclear

  半夹心稀土金属之二的反应（烷基）络合物CP'Ln（CH 2森达3）2（THF）（CP'=η 5 -C 5我4森达3 ; Ln为Y，Lu）的1个当量的双核钨octahydride复杂的[CP * WH的4 ] 2（CP * =η 5 -C 5我5）容易地得到相应的LN / W 2 heterotrimetallic六氢化物络合物CP'Ln（THF）（μ-H）6（WCP *）2（Ln = Y（1a），Lu（1b）），并释放SiMe 4。（C 5 Me 4 R）Ln（CH 2 SiMe 3）2（THF）与双核四氢化配合物[CP * OsH 2 ] 2的相似反应，得到Ln / Os 2杂三金属三氢化物配合物[（CP * Os） （μ-η 5：η 1 -C 5我4 CH 2）锇} LN（C 5我4 R）（THF）（μ-H）3 ]（2A，Ln为Y，R =森达3 ;图2b（Ln ＝ Lu，R ＝ Me），其中Os中心上的CP
• Half-sandwich bis(propiolamidinate) rare-earth metal complexes: synthesis, structure and dissociation of the cyclopentadienyl ligand via competition with an amidinate
  作者：Ling Xu、Yu-Chen Wang、Wen-Xiong Zhang、Zhenfeng Xi

  DOI：10.1039/c3dt52179f

  日期：——

  A comparative study on the stabilizing ability between C5Me4(SiMe3) (Cp′ for short) and amidinate in rare-earth metal complexes is investigated. Cp′ is found to dissociate from half-sandwich bis(propiolamidinate) lanthanides via competition with a propiolamidinate, which clearly shows that the coordinative ability of chelate amidinate is stronger than that of η5-Cp′ under the present conditions.

  研究了稀土金属络合物中C 5 Me 4（SiMe 3）（简写为CP'）与a胺的稳定能力的比较研究。CP'是从半夹心双（propiolamidinate）镧系元素发现解离通过用propiolamidinate，这清楚地表明，螯合物脒基的配位能力比η的更强的竞争5在目前条件下-CP'。
• Selective ammonolysis of half-sandwich rare-earth metal dialkyl and polyhydride complexes: synthesis of polyamido rare-earth complexes having novel structures
  作者：Takanori Shima、Zhaomin Hou

  DOI：10.1039/c0dt00006j

  日期：——

  The scandium dialkyl complex [Cp′Sc(CH2SiMe3)2(THF)] (1-Sc, Cp′ = C5Me4SiMe3) reacts rapidly with ammonia at room temperature to afford selectively a trinuclear hexaamido complex [Cp′Sc(μ-NH2)2]3 (3-Sc) with release of SiMe4. The reaction of the lutetium dialkyl complex [Cp′Lu(CH2SiMe3)2(THF)] (1-Lu) with ammonia under the same conditions gives the analogous hexaamido Lu complex [Cp′Lu(μ-NH2)2]3 (3-Lu) as a major product (92%) together with a tetranuclear octaamido complex [Cp′Lu(μ-NH2)2]4 (4-Lu) as a minor product (8%). In contrast, reaction of tetranuclear rare-earth metal octahydride complexes [Cp′Ln(μ-H)2]4(THF) (Ln = Y (2-Y), Lu (2-Lu)) with ammonia under similar conditions yields selectively the heptaamido/monohydrido complexes [(Cp′Ln)4(μ-NH2)6(μ3-NH2)(μ4-H)] (Ln = Y (5-Y), Lu (5-Lu)), in which a μ4-H ligand remains at the center of the tetrahedral metal framework. Exposure of heptaamido/monohydrido complex 5-Lu to an ammonia atmosphere at room temperature for a long time (two days) affords the octaamido complex 4-Lu quantitatively. The molecular structures of 3-Sc, 3-Lu, 4-Lu, 5-Y, and 5-Lu have been determined by X-ray analyses.

  钪二烷基络合物[Cp′Sc(CH2SiMe3)2(THF)]（1-Sc，Cp′ = C5Me4SiMe3）在室温下与氨迅速反应，生成三核六氨基络合物[Cp′Sc(μ-NH2)2]3（3-Sc），并释放出 SiMe4。在相同条件下，镥二烷基络合物[Cp′Lu(CH2SiMe3)2(THF)]（1-Lu）与氨反应，得到类似的六氨基镥络合物[Cp′Lu(μ- NH2)2]3 （3-Sc）。NH2)2]3（3-Lu）为主要产物（92%），四核八氨基复合物[Cp′Lu(μ-NH2)2]4（4-Lu）为次要产物（8%）。相反，四核稀土金属八氢络合物 [Cp′Ln(μ-H)2]4(THF)（Ln = Y (2-Y)、Lu（2-Lu））在类似条件下与氨反应，可选择性地得到七氨基/一水配合物[(Cp′Ln)4(μ-NH2)6(μ3-NH2)(μ4-H)]（Ln = Y（5-Y），Lu（5-Lu）），其中μ4-H 配体保留在四面体金属框架的中心。将七氨基/一水配合物 5-Lu 在室温氨气环境中长期（两天）暴露，可定量得到八氨基配合物 4-Lu。通过 X 射线分析，确定了 3-Sc、3-Lu、4-Lu、5-Y 和 5-Lu 的分子结构。
• Synthesis and Structure Diversity of Half‐Sandwich Rare Earth Dialkynyl Complexes
  作者：Gang Xiong、Olivier Tardif、Masayoshi Nishiura、Guan Bingtao、Zhaomin Hou

  DOI：10.1002/hlca.202100197

  日期：2022.1

  reactions between half-sandwich rare earth dialkyl complexes (C5Me4SiMe3)Ln(CH2SiMe3)2(THF) (Ln=Sc, Y, Lu) and two equivalents of terminal alkynes such as phenylacetylene and trimethylsilylacetylene in THF generally gave the corresponding THF-coordinated monomeric rare earth dialkynyl complexes, which upon recrystallization from toluene yielded further aggregated alkynyl complexes with partial or full dissociation

  半夹心稀土二炔基配合物对结构和反应性都非常感兴趣，但迄今为止仍未得到充分探索。在这里，我们报告了一种新的半夹心二炔基配合物家族的合成和转化，该配合物带有 C 5 Me 4 SiMe 3配体，其根据金属离子大小、炔烃取代基以及有或没有 THF 配位表现出不同的结构特征。半夹心稀土二烷基配合物(C 5 Me 4 SiMe 3 )Ln(CH 2 SiMe 3 ) 2之间的酸碱反应(THF) (Ln = Sc, Y, Lu) 和两个当量的末端炔烃如苯乙炔和三甲基甲硅烷基乙炔在 THF 中通常产生相应的 THF 配位单体稀土二炔基配合物，在从甲苯中重结晶时产生进一步聚集的炔基配合物，其中部分或 THF 配体完全解离。在苯乙炔的情况下，形成了三聚钇和镥六炔基配合物，其中每对金属原子由两个固态炔基配体桥接，但炔基配体在甲苯溶液中发生快速位点交换。在具有钇和镥的三甲基甲硅烷基乙炔的情况下，由甲苯获得带有两