(Me2Si(η5-Me4C5)((t)BuN))UCl2 | 634591-68-7

• 英文名称: (Me2Si(η5-Me4C5)((t)BuN))UCl2
• CAS: 634591-68-7
• 化学式: C₁₅H₂₇Cl₂NSiU
• 分子量: 558.406
• InChiKey: NFUUMHIRRQJUNB-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  三甲基氯硅烷 、 (Me2Si(η5-Me4C5)((t)BuN))U(NEtMe)2 以 正戊烷 为溶剂， 以84%的产率得到(Me2Si(η5-Me4C5)((t)BuN))UCl2
  参考文献：
  名称：

  新型约束几何有机act离子催化剂的合成及催化性能。Act系元素介导的分子内氢化反应的第一个例子

  摘要：

  的合成，表征，和一系列organoactinide限制几何构型配合物的反应性，（CGC）一种（NRR'）2（CGC =我2的Si（η 5 -Me 4 Ç 5）（吨BUN）;安= Th时，报道了1； An ＝ U，2； R ＝ R′＝ Me，a； R ＝ Et，R′＝ Me，b； R ＝ R′＝ Et，c）。这些络合物是用于氨基烯烃和氨基炔烃的分子内催化加氢胺化/环化的有效预催化剂。使用先前报道的三价有机镧系元素CGC催化系统进行结构和反应性的比较。

  DOI：

  10.1021/om034093f

文献信息

• Constrained Geometry Organoactinides as Versatile Catalysts for the Intramolecular Hydroamination/Cyclization of Primary and Secondary Amines Having Diverse Tethered C−C Unsaturation
  作者：Bryan D. Stubbert、Tobin J. Marks

  DOI：10.1021/ja0665444

  日期：2007.4.1

  A series of "constrained geometry" organoactinide complexes, (CGC)An(NMe)(2) (CGC = Me2Si(eta(5)-Me4C5)((BuN)-Bu-t); An = Th, 1; U, 2), has been prepared via efficient in situ, two-step protodeamination routes in good yields and high purity. Both 1 and 2 are quantitatively converted to the neutrally charged, solvent-free dichlorides (1-Cl-2, 2-Cl-2) and slightly more soluble diiodides (1-I-2, 2-I-2) with excess Me3Si-X (X = Cl, I) in non-coordinating solvents. The new complexes were characterized by NMR spectroscopy, elemental analysis, and (for 1 and 2) single-crystal X-ray diffraction, revealing substantially increased metal coordinative unsaturation vs the corresponding Me2SiCp ''(2)AnR(2) (Cp '' = eta(5)-Me4C5; An = Th, R = CH2(SiMe3), 3; An = U, R = CH2Ph, 4) and Cp'(2)AnR(2) (Cp' = eta(5)-Me5C5 ; An = Th, R = CH2(SiMe3), 5; An = U, R = CH2(SiMe3), 6) complexes. Complexes 1-6 exhibit broad applicability for the intramolecular hydroamination of diverse C-C unsaturations, including terminal and internal aminoalkenes (primary and secondary amines), aminoalkynes (primary and secondary amines), aminoallenes, and aminodienes. Large turnover frequencies (N-t up to 3000 h(-1)) and high regioselectivities (>= 95%) are observed throughout, along with moderate to high diastereoselectivities (up to 90% trans ring closures). With several noteworthy exceptions, reactivity trends track relative 5f ionic radii and ancillary ligand coordinative unsaturation. Reactivity patterns and activation parameters are consistent with a reaction pathway proceeding via turnover-limiting CC/CC insertion into the An-N sigma-bond.