ansa-Me2SiCp''2Th''Bu2 | 89597-07-9

• 英文名称: ansa-Me2SiCp''2Th''Bu2
• 英文别名: (Me2Si(C5Me4)2)2ThBu2
• CAS: 89597-07-9
• 化学式: C₂₈H₄₈SiTh
• 分子量: 644.813
• InChiKey: NGZQDFKGWXFYIR-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：

  ansa-Me2SiCp''2Th''Bu2 在 hydrogen 作用下， 以 正庚烷 为溶剂， 生成
  参考文献：
  名称：

  操纵有机act配位不饱和和立体化学。螯合双（聚甲基环戊二烯基）烃基和氢化物的性质

  摘要：

  DOI：

  10.1021/om00083a036
• 作为产物：
  描述：

  ansa-Me2SiCp''2ThCl2 在 n-butyllithium 作用下， 以 乙二醇二甲醚 为溶剂， 以30-50的产率得到ansa-Me2SiCp''2Th''Bu2
  参考文献：
  名称：

  操纵有机act配位不饱和和立体化学。螯合双（聚甲基环戊二烯基）烃基和氢化物的性质

  摘要：

  DOI：

  10.1021/om00083a036

文献信息

• Metal, bond energy, and ancillary ligand effects on actinide-carbon .sigma.-bond hydrogenolysis. A kinetic and mechanistic study
  作者：Zerong Lin、Tobin J. Marks

  DOI：10.1021/ja00260a007

  日期：1987.12

  with Cp'/sub 2/ThCH/sub 2/C(CH/sub 3/)/sub 2/CH/sub 2/ approx. = Cp'/sub 2/U(CH/sub 2/-t-Bu) (too rapid to measure accurately) > Cp'/sub 2/Th(CH/sub 2/-t-Bu)(OCH(t-Bu)/sub 2/) = Cp'/sub 2/Th(CH/sub 2/-t-Bu)(O-t-Bu) > Cp'/sub 2/Th(CH/sub 2/-t-Bu)(Cl) > Me/sub 2/Si(Me/sub 4/C/sub 5/)/sub 2/Th(n-Bu)/sub 2/ > Cp'/sub 2/Th(n-Bu)/sub 2/ approx. = Cp'/sub 2/ThMe/sub 2/ > Cp'/sub 2/Th(Me)(O/sub 3/SCF/sub 3/) >

  报道了锕系烃基配体氢解 (An-R + H/sub 2/ ..-->.. An-H + RH) 的动力学机理研究。对于复数 Cp'/sub 2/TH(CH/sub 2/-t-Bu)(Ot-Bu)(Cp' = eta/sup 5/-Me/sub 5/C/sub 5/)，速率定律在有机锕系元素中为一阶，在 H/sub 2/ 中为一阶，其中 k/sub H2/k/sub D2/ = 2.5 (4) 和 k/sub THF/k/sub 甲苯/ = 2.9 (4) . 对于一系列配合物，氢解速率的范围约为 10/sup 5/ 与 Cp'/sub 2/ThCH/sub 2/C(CH/sub 3/)/sub 2/CH/sub 2/ 约。= Cp'/sub 2/U(CH/sub 2/-t-Bu)（速度太快而无法准确测量）> Cp'/sub 2/Th(CH/sub 2/-t-Bu)(OCH(t- Bu)/sub
• Organoactinides Promote the Dimerization of Aldehydes: Scope, Kinetics, Thermodynamics, and Calculation Studies
  作者：Manab Sharma、Tamer Andrea、Nigel J. Brookes、Brian F. Yates、Moris S. Eisen

  DOI：10.1021/ja105696p

  日期：2011.2.9

  Surprising catalytic activities have been found for the actinide complexes Cp*2ThMe2 (1), Th(NEtMe)(4) (2), and Me2SiCp '' Th-2(C4H9)(2)(3) toward oxygenated substrates. During the catalytic dimerization of benzaldehydes to their corresponding esters, complexes 1 and 2 gave 65 and 85% yield in 48 h, respectively, while the geometry-constrained complex 3 gave 96% yield in 24 h. Exploring the effect of substituents on benzaldehyde, it has been found that, in general, electron-withdrawing groups facilitate the reaction. Kinetic study with complexes 1 and 3 reveals that the rate of the reaction is first order in catalyst and substrate, which suggests the rate equation "rate = k[catalyst](1)-[aldehyde](1)". The activation energy of the reaction was found to be 7.16 +/- 0.40 and 3.47 +/- 0.40 kcal/mol for complexes 1 and 3 respectively, which clearly indicates the advantage of the geometry-constrained complex. Astonishing are the reactivity of the organoactinide complexes with oxygen-containing substrates, and especially the reactivity of complex 3, toward the dimerization of substrates like p-methoxybenzaldehyde, m/p-nitrobenzaldehyde, and furanaldehyde and the reactivity toward the polymerization of terephthalaldehyde. Density functional theory mechanistic study reveals that the catalytic cycle proceeds via an initially fourcentered transition state (+6 kcal/mol), followed by the rate-determining six-centered transition state (+13.5 kcal/mol), to yield thermodynamically stable products.
• Organoactinides—novel catalysts for demanding chemical transformations
  作者：Aswini K. Dash、Ylia Gurevizt、Ji Quan Wang、Jiaxi Wang、Moshe Kapon、Moris S. Eisen

  DOI：10.1016/s0925-8388(02)00307-9

  日期：2002.10

  The catalytic effect obtained by opening the coordination sphere of the organoactinide complex is presented. Replacing the pentamethylcyclopentadienyl ligand in Cp-2*ThCl2 (Cp*=C5Me5) by the bridge ligation [Me2SiCp2"](2-) 2[Li](+) (Cp" = C5Me4) affords the synthesis of ansa-Me2SiCp2"ThCl2, which reacts with two equiv of BuLi affording the corresponding dibutyl complex ansa-Me2SiCp2"Th"Bu-2. This latter complex was found to be an active catalyst for the dimerization of terminal alkynes, and in the hydrosilylation of terminal alkynes with PhSi3. In both processes a large chemoselectivity and regioselectivity are achieved due to the hindered equatorial plane, attributed to the disposition of the methyl groups in the bridge ligation, forcing the incoming substrates to react with a specific regiochemistry. (C) 2002 Elsevier Science B.V. All rights reserved.
• Manipulation of organoactinide coordinative unsaturation. Synthesis, structures, and reactivity of thorium hydrocarbyls and hydrides with chelating bis(tetramethylcyclopentadienyl) ancillary ligands
  作者：Carol M. Fendrick、Larry D. Schertz、Victor W. Day、Tobin J. Marks

  DOI：10.1021/om00098a021

  日期：1988.8