(η⁵-C₅Me₄(SiMe₃))′Y(CH₂SiMe₃)₂(thf) | 221327-70-4

• 英文名称: (η⁵-C₅Me₄(SiMe₃))′Y(CH₂SiMe₃)₂(thf)
• 英文别名: [(η⁵-C₅Me₄(SiMe₃))Y(CH₂SiMe₃)₂(thf)]；[(C₅Me₄SiMe₃)Y(CH₂SiMe₃)₂(THF)]；Cp′Y(CH₂SiMe₃)₂(thf)；[(η5-trimethyl(2,3,4,5-tetramethyl-2,4-cyclopentadienyl)silane(-H))Y(trimethylsilylmethyl)2(tetrahydrofuran)]；[Y(η(5)-C5Me4SiMe3)(CH2SiMe3)2(THF)]；(η5-(C5Me4)SiMe3)Y(CH2SiMe3)2(THF)
• CAS: 221327-70-4
• 化学式: C₂₄H₅₁OSi₃Y
• 分子量: 528.831
• InChiKey: YJNIKCYBTVWFEY-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：

  (η⁵-C₅Me₄(SiMe₃))′Y(CH₂SiMe₃)₂(thf) 、 tetra-μ-hydrido-bis[(pentamethyl-η5-cyclopentadienyl)ruthenium] 以 苯 为溶剂， 以62%的产率得到[(C5Me5)Ru]4(C5Me3CH2SiMe3)Y(μ-H)7
  参考文献：
  名称：

  基于半三明治稀土部分的稀土/ d-过渡金属杂多金属多羟基化合物络合物

  摘要：

  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

  DOI：

  10.1021/om900024q
• 作为产物：
  描述：

  [(C5Me4SiMe3)Y(μ-H)(CH2SiMe3)(THF)]2 以 苯 为溶剂， 生成 (η⁵-C₅Me₄(SiMe₃))′Y(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
• 作为试剂：
  描述：

  4-甲基-1-戊烯 、 N,N-二甲基苯胺 在 (η⁵-C₅Me₄(SiMe₃))′Y(CH₂SiMe₃)₂(thf) 、 三苯碳四(五氟苯基)硼酸盐 作用下， 以 甲苯 为溶剂， 反应 72.0h， 以75%的产率得到N,N-dimethyl-2-(4-methylpentan-2-yl)aniline
  参考文献：
  名称：

  通过钇催化剂将 N,N-二甲基苯胺与烯烃进行邻位选择性 C–H 加成†

  摘要：

  首次使用阳离子半夹心钇催化剂实现了通过C-H 加成到烯烃上的N , N-二甲基苯胺的高效选择性邻位烷基化。该方案为合成具有支链烷基取代基的新叔苯胺衍生物家族提供了一种简单且原子经济的路线，否则很难获得这些衍生物。 DFT计算研究表明，钇原子和NMe 2基团之间的相互作用起着重要作用，并且通过σ键复分解途径的分子内C-H激活是速率决定步骤，这与实验KIE观察结果一致。

  DOI：

  10.1039/c6sc00833j

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。
• Cyclopentadienyl-Like Ligand as a Reactive Site in Half-Sandwich Bis(amidinato) Rare-Earth-Metal Complexes: An Efficient Application in Catalytic Addition of Amines to Carbodiimides
  作者：Peng-Hui Wei、Ling Xu、Li-Cheng Song、Wen-Xiong Zhang、Zhenfeng Xi

  DOI：10.1021/om5002793

  日期：2014.6.9

  excellent catalytic activity for the addition of amines to carbodiimides, yielding the corresponding guanidines. Isolation, structural characterization, and catalytic application of the binuclear lutetium amido complex showed clearly that the catalytic cycle was initiated by the dissociation of Cp′. These results demonstrated that Cp′, for the first time, acted as a reactive site to yield the active Ln–N

  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。
• Cleavage of carbon monoxide and C-C bond formation promoted by rare-earth/ruthenium heterobimetallic hydride complexes
  作者：Daisuke Kawai、Takanori Shima、Masayoshi Nishiura、Zhaomin Hou

  DOI：10.1016/j.jorganchem.2017.02.042

  日期：2017.10

  [(C5Me4SiMe3)Y(DME)(μ-H)2(μ-η1:η1-C6H4PPh2)RuCp*] (R = H, Me; Cp* = C5Me5) with carbon monoxide. C–O bond cleavage and C–C bond formation, as well as P–C bond cleavage of the phosphine ligand occurred through the cooperation of two different metal centers. Dependence of the reaction pattern on the substituents of the phosphine ligands was also observed.

  由稀土和d-过渡金属组成的杂多金属氢化物配合物有望表现出独特的反应性，因为它们有潜力显示出基本不同类型的金属中心的协同效应。这里，我们报告稀土类的反应/钌的异二氢化物的[Cp *路（THF）（μ -H）2（μ - η 1：η 1 -CHRP（CH 2 R）2）RuCp *]和[（ ç 5我4森达3）Y（DME）（μ -H）2（μ - η 1：η1 -C 6 H 4 PPh 2）RuCp *]（R = H，Me; Cp * = C 5 Me 5）。膦配体的C–O键断裂和C–C键形成以及P–C键断裂是通过两个不同的金属中心的协同作用而发生的。还观察到反应模式对膦配体的取代基的依赖性。
• 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'。
• Synthesis and Characterization of a Tetranuclear Hydride Cluster of Yttrium [{(η⁵‐C₅Me₄SiMe₃)Y}₄(μ‐H)₄(μ₃‐H)₄(THF)₂]
  作者：Kai C. Hultzsch、Peter Voth、Thomas P. Spaniol、Jun Okuda

  DOI：10.1002/zaac.200300063

  日期：2003.7

  Hydrogenolysis of the dialkyl complexes [Y(η⁵‐C₅Me₄SiMe₂R)(CH₂SiMe₃)₂(THF)] (1a, R = Me; 1b, R = Ph) results in the formation of the tetranuclear dihydrido complexes [(η⁵‐C₅Me₄SiMe₂R)Y}₄(μ‐H)₄(μ₃‐H)₄(THF)₂] (2a, R = Me; 2b, R = Ph), characterized by NMR spectroscopy. 2a was studied by single crystal X‐ray diffraction. In the solid state, an unsymmetrical tetrahedral configuration of four [Y(η⁵‐C₅Me₄SiMe₃)] units is observed, two of which contain each one molecule of THF. Each yttrium atom is bonded to two μ₂‐ as well as three μ₃‐bridging hydrido ligands.

  摘要氢解二烷基络合物 [Y(η5-C5Me4SiMe2R)(CH2SiMe3)2(THF)]（1a，R = Me；1b，R = Ph），从而形成四核二氢配合物[(η5-C5Me4SiMe2R)Y}4(μ-H)4(μ3-H)4(THF)2]（2a，R = Me；2b，R = Ph），并通过核磁共振光谱进行表征。对 2a 进行了单晶 X 射线衍射研究。在固态下，观察到由四个[Y(η5-C5Me4SiMe3)]单元组成的非对称四面体构型，其中两个单元各含有一分子 THF。每个钇原子都与两个 μ2- 和三个 μ3 桥接的氢化物配位体结合。