(Me2Si(C5Me4)2)2Th(n-butyl alcoholate)2 | 1264111-87-6

• 英文名称: (Me2Si(C5Me4)2)2Th(n-butyl alcoholate)2
• CAS: 1264111-87-6
• 化学式: C₂₈H₄₈O₂SiTh
• 分子量: 676.812
• InChiKey: NFVKRROGTCRXMY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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

• 作为产物：
  描述：

  ansa-Me2SiCp''2Th''Bu2 、 正丁醇 以 甲苯 为溶剂， 以75%的产率得到(Me2Si(C5Me4)2)2Th(n-butyl alcoholate)2
  参考文献：
  名称：

  Organoactinides Promote the Dimerization of Aldehydes: Scope, Kinetics, Thermodynamics, and Calculation Studies

  摘要：

  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.

  DOI：

  10.1021/ja105696p