[(C₅Me₅)Lu(CH₂SiMe₃)₂(THF)] | 717100-21-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: [(C₅Me₅)Lu(CH₂SiMe₃)₂(THF)]
• 英文别名: [Cp*Lu(CH₂SiMe₃)₂(THF)]；lutetium(3+);methanidyl(trimethyl)silane;oxolane;1,2,3,4,5-pentamethylcyclopenta-1,3-diene
• CAS: 717100-21-5
• 化学式: C₂₂H₄₅LuOSi₂
• 分子量: 556.737
• InChiKey: CZGAEOUGETXDFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.14
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tetra-μ-hydrido-bis[(pentamethyl-η5-cyclopentadienyl)ruthenium] 、 [(C₅Me₅)Lu(CH₂SiMe₃)₂(THF)] 以 苯 为溶剂， 以44%的产率得到[(C5Me5)Ru]4(C5Me4CH2)Lu(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：

  Lu(trimethylsilylmethyl)3(tetrahydrofuran)2 、 1,2,3,4,5-五甲基环戊二烯 以 甲苯 为溶剂， 以77%的产率得到[(C₅Me₅)Lu(CH₂SiMe₃)₂(THF)]
  参考文献：
  名称：

  Synthesis and Characterization of (Mono)pentamethylcyclopentadienyl Lutetium Complexes:  Formation of Bipyridyl-Stabilized Alkyls, Anilides, and Terminal Acetylides

  摘要：

  The alkyl complex [Lu(CH2SiMe3)(3)(THF)(2)] reacts with pentamethylcyclopentadiene (Cp*H), giving [CP*Lu(CH2SiMe3)(2)(THF)] (1). Complex 1 reacts with 1,2-dimethoxyethane (DME), affording [Cp*Lu(CH2SiMe3)(2)(DME)] (2). Complex 1 also reacts with 2,2'-bipyridine (bipy) to give [Cp*Lu(CH2SiMe3)(2)(bipy)] (3). The dialkyl complex 3 reacts with 1.0 equiv of 2,6-diisopropylaniline to give the mixed alkyl-anilide [Cp*Lu(NHAr)(CH2SiMe3)(bipy)] (4) (Ar = 2,6-Pri(2)C(6)H(3)) and the bis(anilide) [Cp*Lu(NHAr)(2)(bipy)] (5) in a 1.0:0.09 ratio. Complex 5 can be independently synthesized in high yield by treatment of 3 with 2.0 equiv of 2,6-diisopropylaniline or 4 with 1.0 equiv of 2,6-diisopropylaniline. Complex 3 also reacts with 2.0 equiv of phenylacetylene to afford dimeric [{Cp*Lu(CCPh)(bipy)}(2)(mu-eta(2) : eta(2)-PhC4Ph)] . 2(C6H6) (6). Complex 6 reacts with THF and pyridine (py), giving terminal (bis)acetylide complexes [Cp*Lu(CCPh)(2)(bipy)(THF)] (7) and [Cp*Lu(CCPh)(2)(bipy)(py)] (8), respectively. The solid-state structures of 1, 2, 4, 5, 6, and 8 are reported.

  DOI：

  10.1021/om0497700

文献信息

• Reactivity of (C₅Me₅)Lu(CH₂SiMe₃)₂(THF) with Pyridine Ring Systems:  Synthesis and Structural Characterization of an η²-(N,C)-Pyridyl (Mono)pentamethylcyclopentadienyl Lutetium(III) Complex
  作者：Kimberly C. Jantunen、Brian L. Scott、John C. Gordon、Jaqueline L. Kiplinger

  DOI：10.1021/om0702330

  日期：2007.5.1

  Reaction of (C5Me5)Lu(CH2SiMe3)2(THF) with pyridine results in the activation of an ortho C−H bond to form the corresponding η2-(N,C)-pyridyl complex with elimination of SiMe4. This is a rare example of pyridine metalation at a lanthanide metal center in the absence of a bent metallocene framework. The η2-(N,C)-pyridyl coordination mode was confirmed by X-ray crystallographic analysis. The pyridyl

  的（C反应5我5）路（CH 2森达3）2（THF）与邻位的CH键的激活吡啶结果形成相应的η 2 - （N，C） -吡啶基配合物与消除SiMe 4。在不存在弯曲的茂金属骨架的情况下，这是在镧系金属中心发生吡啶金属化的罕见例子。的η 2 - （N，C） -吡啶基配位模式通过X射线晶体分析证实。吡啶基络合物采用C 5 Me 5扭曲的方锥几何形状位于顶端位置的吡啶单元和吡啶基配体以及剩余的配体位于基面。同位素标记研究表明，CH键的活化与σ键复分解机制是一致的。
• Activation and Dehydrogenative Silylation of the C–H Bonds of Phosphine-coordinated Ruthenium in Lu/Ru Heteromultimetallic Hydride Complexes
  作者：Takanori Shima、Zhaomin Hou

  DOI：10.1246/cl.2008.298

  日期：2008.3.5

  The reaction of half-sandwich lutetium dialkyl complex Cp∗Lu(CH2SiMe3)2(THF) (Cp∗= C5Me5) with ruthenium–trihydrido–phosphine complexes Cp∗Ru(PR3)H3 (R3 = Ph3, Ph2Me, PhMe2, and Me3) at 50 °C afforded the corresponding Lu/Ru heterobimetallic dihydride complexes, which was accompanied by selective C–H bond activation of the phosphine ligand. The reaction of such a resulting phosphinomethyl-bridged Lu/Ru complex with PhSiH3 led to selective dehydrogenative silylation at the “CH2” unit.

  半夹心镥二烷基络合物 Cp*Lu( SiMe3)2(THF) (Cp*= C5Me5) 与钌三氢膦络合物 Cp*Ru(PR3)H3 (R3 = Ph3、Ph2Me、PhMe2 和 Me3) 的反应）在50℃下得到相应的Lu/Ru异双金属二氢化物配合物，伴随着膦配体的选择性C-H键活化。由此产生的膦甲基桥联的 Lu/Ru 络合物与 PhSiH3 的反应导致“CH2”单元选择性脱氢甲硅烷基化。
• 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。
• Dearomatization and Functionalization of Terpyridine by Lutetium(III) Alkyl Complexes
  作者：Kimberly C. Jantunen、Brian L. Scott、P. Jeffrey Hay、John C. Gordon、Jaqueline L. Kiplinger

  DOI：10.1021/ja061161r

  日期：2006.5.1

  Lutetium(III)-bis(alkyl) and -tris(alkyl) fragments supported by either 2,2':6',2' '-terpyridine or 4,4',4' '-tri-tert-butyl-2,2':6',2' '-terpyridine are not stable and undergo facile 1,3-alkyl migration under ambient conditions resulting in dearomatization and ortho (2' or 6') functionalization of the terpyridyl ligand, clearly demonstrating that the terpyridyl ligand framework is not as innocent as previously thought.