(Me2Si(η5-Me4C5)((t)BuN))U(NMe2)2 | 634591-66-5

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (Me2Si(η5-Me4C5)((t)BuN))U(NMe2)2
• 英文别名: [(Me2Si(η5-Me4C5)(t-BuN))U(NMe)2]；[(Me2Si(η5-Me4C5)(tBuN)U(NMe2)2]；tert-butyl-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl]azanide;dimethylazanide;uranium(4+)
• CAS: 634591-66-5
• 化学式: C₁₉H₃₉N₃SiU
• 分子量: 575.653
• InChiKey: BWEUGNKXHSIEMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.46
• 重原子数：
  24
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  碘代三甲硅烷 、 (Me2Si(η5-Me4C5)((t)BuN))U(NMe2)2 以 正戊烷 为溶剂， 以99%的产率得到
  参考文献：
  名称：

  Constrained Geometry Organoactinides as Versatile Catalysts for the Intramolecular Hydroamination/Cyclization of Primary and Secondary Amines Having Diverse Tethered C−C Unsaturation

  摘要：

  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.

  DOI：

  10.1021/ja0665444
• 作为产物：
  描述：

  lithium dimethylamide 、 氯化铀 、 N-[dimethyl-(2,3,4,5-tetramethylcyclopenta-1,4-dien-1-yl)silyl]-2-methylpropan-2-amine 以 四氢呋喃 、 正戊烷 为溶剂， 以57.9%的产率得到(Me2Si(η5-Me4C5)((t)BuN))U(NMe2)2
  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

• Mechanistic Investigation of Intramolecular Aminoalkene and Aminoalkyne Hydroamination/Cyclization Catalyzed by Highly Electrophilic, Tetravalent Constrained Geometry 4d and 5f Complexes. Evidence for an M−N σ-Bonded Insertive Pathway
  作者：Bryan D. Stubbert、Tobin J. Marks

  DOI：10.1021/ja0675898

  日期：2007.5.1

  conventional (CGC)MR2 (M = Th, R = NMe2, 1; M = U, R = NMe2, 2; M = Zr, R = Me, 3), (Me2SiCp' '2)UBn2 (Cp' ' = eta5-Me4C5; Bn = CH2Ph, 4), Cp'2AnR2 (Cp' = eta5-Me5C5; R = CH2SiMe3; An = Th, 5, U, 6), and analogous organolanthanide complexes. Deuterium KIEs measured at 25 degrees C in C6D6 for aminoalkene D2NCH2C(CH3)2CH2CHCH2 (11-d2) with precatalysts 2 and 2-Cl indicate that kH/kD = 3.3(5) and 2.6(4), respectively

  介绍了由四价有机锕系元素和有机锆配合物催化的分子内加氢胺化/环化的机理研究。一系列选择性取代的受限几何络合物，(CGC)M(NR2)Cl (CGC = [Me2Si(eta5-Me4C5)(tBuN)]2-; M = Th, 1-Cl; U, 2-Cl; R = SiMe3; M = Zr, R = Me, 3-Cl) 和 (CGC)An(NMe2)OAr (An = Th, 1-OAr; An = U, 2-OAr)，已通过原位脱氨（络合物）制备1-2) 或盐复分解 (3-Cl) 具有高纯度和优异的收率，并且被发现是分子内伯和仲氨基炔和氨基烯烃加氢胺化/环化的活性预催化剂。由这些复合物介导的环化反应的底物反应趋势、速率规律和活化参数实际上与更传统的 (CGC) MR2 相同 (M = Th, R = NMe2, 1; M = U, R = NMe2, 2; M = 锆，R = Me, 3)