(pentamethylcyclopentadienyl)2SmCH(TMS)2 | 98720-37-7

• 英文名称: (pentamethylcyclopentadienyl)2SmCH(TMS)2
• 英文别名: (η(5)-C5Me5)Sm(CH(SiMe3)2)；(η5-Me5C5)2SmCH(Me3Si)2；(η5-Me5C5)2SmCH(TMS)2；(C5Me5)2SmCH(SiMe3)2；Cp*2SmCH(SiMe3)2；Cp*2SmCH(TMS)2
• CAS: 98720-37-7
• 化学式: C₂₇H₄₉Si₂Sm
• 分子量: 580.217
• InChiKey: SHASQGZRPXRCLB-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：

  (pentamethylcyclopentadienyl)2SmCH(TMS)2 在 H₂ 作用下， 以 正戊烷 为溶剂， 生成 [(pentamethylcyclopentadienyl)2Sm(μ-H)]2
  参考文献：
  名称：

  Highly reactive organolanthanides. Systematic routes to and olefin chemistry of early and late bis(pentamethylcyclopentadienyl) 4f hydrocarbyl and hydride complexes

  摘要：

  DOI：

  10.1021/ja00312a050
• 作为产物：
  描述：

  [(C5Me5)2Sm((μ-Ph)2BPh2)] 、 bis(trimethylsilyl)methyllithium 以 苯 为溶剂， 以94%的产率得到(pentamethylcyclopentadienyl)2SmCH(TMS)2
  参考文献：
  名称：

  非溶剂化镧系金属茂阳离子 [(C5Me5)2Ln][BPh4]：多重合成、结构表征和反应性，包括 (C5Me5)3Nd1 的形成

  摘要：

  二价 (C5Me5)2Sm 在甲苯中与 AgBPh4 反应形成 [(C5Me5)2Sm][BPh4], 1, in ca. 60% 的收率。1 的固态结构由三价 (C5Me5)2Sm 弯曲茂金属单元组成，其平均 Sm-C(C5Me5) 距离为 2.702(3)，该距离朝向 [BPh4]- 阴离子的两个苯环2.825(3) 和 2.917(3) A Sm-C(o-Ph) 距离。1 也可以通过 Et3NHBPh4 在芳烃溶剂中与三价钐前体 (C5Me5)2Sm[CH(SiMe3)2]（>50% 产率）和 (C5Me5)2Sm(η3-CH2CHCH2) (2) (>95 ％ 屈服）。1 在苯中与 LiCH(SiMe3)2 反应生成 (C5Me5)2Sm[CH(SiMe3)2]，产率超过 95%。1 与 KC5Me5 在苯中的反应构成了空间拥挤络合物 (C5Me5)3Sm 的新合成，其产率超过 90%。该反应为制备

  DOI：

  10.1021/ja980534o
• 作为试剂：
  描述：

  1,2-diphenyldisilane 在 (pentamethylcyclopentadienyl)2SmCH(TMS)2 作用下， 以 氘代苯 为溶剂， 反应 48.0h， 以10%的产率得到三苯基硅烷
  参考文献：
  名称：

  Samarium-mediated redistribution of silanes and formation of trinuclear samarium–silicon clusters

  摘要：

  The samarium complex Cp(2)*SmCH(SiMe(3))(2) (Cp* = C(5)Me(5)), unlike the related alkyls Cp(2)*LnCH(SiMe(3))(2) (Ln = Y, Nd), mediates the redistribution of hydrosilanes while being converted to trisamarium clusters, including Cp(6)*Sm-3(mu-SiH3)(mu(3)-eta(1),eta(1),eta(2)-SiH2-SiH2).

  DOI：

  10.1039/cc9960002459

文献信息

• <b>Organo-f</b>^{<b><i>n</i></b>}<b>,d</b>^<b>0</b><b>-Mediated Synthesis of Amine-Capped Polyethylenes. Scope and Mechanism</b>
  作者：Smruti B. Amin、SungYong Seo、Tobin J. Marks

  DOI：10.1021/om700831t

  日期：2008.6.9

  of the structure H(CH2CH2)nNRR′, where an efficient chain-transfer agent is defined as a reagent that both terminates polymer chain growth and facilitates reinitiation of polymer chain growth. Under the conditions investigated, primary amines are found to be the most inert toward Cp′2La-mediated polymerizations, affording no detectable insertion products, while di-sec-butylamine and N,N-bis(trimethylsilyl)amine

  研究了不同布朗斯台德酸度和空间位阻的胺作为链转移剂，以通过有机镧系元素介导的烯烃聚合过程将聚烯烃官能化。乙烯均聚与活化的CP'进行2 LnCH硅烷（Si（CH 3）3）2（CP'=η 5 -Me 5 Ç 5在苯胺的存在下预催化剂; Ln为La，Sm或Y，Lu）的Ñ丙胺，ñ，ñ -双（三甲基硅烷基）胺，二仲丁胺，ñ -叔丁基（三甲基硅基）胺，二-异丙胺和二环己胺。在这些胺的存在下，观察到高达10 4 g聚合物/（Ln·atm乙烯·h摩尔）的聚合活性和窄的产物聚合物多分散性，这与单中心聚合过程一致。胺链转移效率如下趋势Ç 6 ħ 5 NH 2 ≈ Ñ ç 3 ħ 7 NH 2 << [SI（CH 3）3 ] 2 NH≈秒卜2 NH < Ñ -吨卜[硅（CH 3）3 ] NH≈我镨2 NH
• Organo-f-element thermochemistry. Absolute metal-ligand bond disruption enthalpies in bis(pentamethylcyclopentadienyl)samarium hydrocarbyl, hydride, dialkylamide, alkoxide, halide, thiolate, and phosphide complexes. Implications for organolanthanide bonding and reactivity
  作者：Steven P. Nolan、David Stern、Tobin J. Marks

  DOI：10.1021/ja00202a027

  日期：1989.9

  in the series Cpprime}sub 2}Sm-R/X (Cpprime} = eta}sup 5}-(CHsub 3})sub 5}Csub 5}) have been measured by iodinolytic and alcoholytic isoperibol titration calorimetry of Cpprime}sub 2}Sm/(Cpprime}sub 2}Sm-I)sub n}, (Cpprime}sub 2}Sm-Osup t}Bu)sub 2}/Cpprime}sub 2}Sm-R/X ensembles in toluene. A variety of Sm-centered ligand transposition and oxidative addition/reductive elimination processes

  Cpprime}sub 2}Sm-R/X (Cpprime} = eta}sup 5}-(CHsub 3})sub 5}C 系列中的绝对钐-配体键断裂焓sub 5}) 已通过 Cpprime}sub 2}Sm/(Cpprime}sub 2}Sm-I)sub n}, (Cpprime}sub 2}Sm-Osup t}Bu)sub 2}/Cpprime}sub 2}Sm-R/X 在甲苯中的集合。根据现有数据分析了各种以 Sm 为中心的配体换位和氧化加成/还原消除过程。强 Sm-异元素键的形成对驱动力做出了重要贡献。通过双核 Sm(II) 产量} Sm(III) 氧化加成过程的烃官能化预计仅在特殊情况下才会放热。
• Synthesis of Sm−SiH₃ Complexes via σ-Bond Metathesis of the Si−C Bond of Phenylsilane
  作者：Ivan Castillo、T. Don Tilley

  DOI：10.1021/om000516r

  日期：2000.11.1

  Reaction of PhSiH3 with the samarium complexes Cp*2SmCH(SiMe3)2 (1) and [Cp*2Sm(μ-H)]2 (8) (Cp* = C5Me5) leads to redistribution at silicon, yielding benzene, silane, Ph2SiH2, Ph3SiH, and dehydrocoupling products. Cleavage of the Si−C bond of PhSiH3 is accompanied by formation of the lanthanide hydrosilyl complex [Cp*2SmSiH3]3 (2). Complex 2 activates the S−O bond of dimethyl sulfoxide (DMSO) to form

  PhSiH 3与mar络合物Cp * 2 SmCH（SiMe 3）2（1）和[Cp * 2 Sm（μ-H）] 2（8）（Cp * = C 5 Me 5）的反应导致硅上的重新分布生成苯，硅烷，Ph 2 SiH 2，Ph 3 SiH和脱氢偶联产物。PhSiH 3的Si-C键断裂伴随着镧系元素氢甲硅烷基络合物[Cp * 2 SmSiH 3 ] 3（2）的形成。复杂2激活二甲基亚砜（DMSO）的S-O键以形成桥连物种Cp * 2 Sm（DMSO）OSiH 2 OSm（DMSO）Cp * 2（3）。硬路易斯碱Ph 3 PO和HMPA（HMPA =（Me 2 N）3 PO）与2反应生成碱加合物Cp * 2 SmSiH 3（OPPh 3）（4）和Cp * 2 SmSiH 3（HMPA）（5）。配合物5热分解，尽管不是很干净，但会分解为Cp * 2 Sm [OP（NMe 2）2]（HMPA）（6）的收率低
• Neutral lanthanide silyl complexes via σ-bond metathesis reactions
  作者：Nora S. Radu、T. Don Tilley、Arnold L. Rheingold

  DOI：10.1016/0022-328x(95)06088-e

  日期：1996.6

  The alkyl complexes Cp2∗LnCH(SiMe3)2 () and Cp2″LnCH(SiMe3)2 (Cp″ = η5 -C5Me4Et; Ln  Sn, Nd) react with neat H2Si(SiMe3)2 (ca. 5 equivalents) at 85 °C to give the new silyl complexes Cp2∗LnSiH(SiMe3)2 ( (). These neutral silyl complexes have been completely characterized, and are monometic in pentane solution at room temperature. The structure of 3 reveals that this compound forms dimers in the solid

  的烷基配合物的CP 2 * LnCH（森达3）2（）1和CP 2 “LnCH（森达3）2（CP”= η 5 -C 5我4的Et; LN锡，Nd）的用纯反应1h 2的Si（ SiMe 3）2（约5当量）在85°C时得到新的甲硅烷基络合物CP 2 * LnSiH（SiMe 3）2（（）。这些中性甲硅烷基络合物已被完全表征，并且在室温下于戊烷溶液中呈单体态温度。结构3揭示了通过分子间Sm3CH此化合物形成二聚体在固态3 Si相互作用。在SmSi键长3是3.052（8）。最初的反应性研究表明LnSi键具有高反应性。
• Organolanthanide-Catalyzed Imine Hydrogenation. Scope, Selectivity, Mechanistic Observations, and Unusual Byproducts
  作者：Yasushi Obora、Tetsuo Ohta、Charlotte L. Stern、Tobin J. Marks

  DOI：10.1021/ja963775+

  日期：1997.4.1

  In this paper we report the Cp'(2)Ln/Me2SiCp''(2)Ln-catalyzed (Cp' = eta(5)-Me5C5; Cp'' = eta(5)-Me4C5) hydrogenation of acyclic imines to yield the corresponding amines. At 190 psi of H-2, the observed turnover frequencies (h(-1)) (100:1 substrate:catalyst ratio, Cp'(2)Ln, temperature (degrees C)) are (1) (N-benzylidene(methyl)amine, Ln = La, 50) 0.03; (Ln = Sm, 90) 1.0; (Ln = Sm + PhSiH3, 90) 2.2; (Ln = Lu, 90) 0.60; (2) (N-benzylideneaniline, Ln = Sm, 90) 0.10; (3) (N-benzylidene(trimethylsilyl)amine, Ln = Sm, 90) 0.40; (4) (N-(alpha-methylbenzylidene) (methyl)amine, Ln = Sm, 90)0.20; (5) (N-(alpha-methylbenzylidene) (benzyl)amine, Ln = Sm, 90) 0.70. The stoichiometric reaction of N-benzylidene (methyl) amine with Cp'2SmCH(SiMe3)(2) or (Cp'2SmH)(2) yields an orthometalated Cp'Sm-2-substrate complex which undergoes either hydrogenolysis/hydrogenation or competing C=N insertion of a second substrate molecule to yield a Cp'Sm-2-imine-amido complex with a seven-membered chelate ring. The stoichiometric reaction of 2-methyl-1-pyrroline with Cp'2SmCH(SiMe3)(2) or (Cp'2SmH)(2) yields a Cp'Sm-2-imine-amido complex in which two substrate molecules have been coupled to form a six-membered chelate ring (characterized by X-ray diffraction). The stoichiometric reaction of N-benzylidene(trimethylsilyl)amine with (Cp'2SmH)(2) yields a desilylated Cp'Sm-2-imine-amido complex with a four-membered Sm(NSiMe3)(CPh)N=CHPh chelate ring (characterized by X-ray diffraction). Additional heating of this product under H-2 yields S-6-symmetric (Cp'2SmCN)(6), which contains an unusual chairlike 18-membered (SmCN)(6) ring (characterized by X-ray diffraction).