1,4,7-tris(3-adamantyl-5-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane | 666738-27-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,4,7-tris(3-adamantyl-5-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane
• 英文别名: (2-adamantyl-4-tert-butylphenol)3(triazacyclononane)
• CAS: 666738-27-8
• 化学式: C₆₉H₉₉N₃O₃
• 分子量: 1018.56
• InChiKey: DWGHRGVAKMKAHR-KWNWFAQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.92
• 重原子数：
  75.0
• 可旋转键数：
  9.0
• 环数：
  16.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  70.41
• 氢给体数：
  3.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  1,4,7-tris(3-adamantyl-5-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane 、 tris(bis(trimethylsilyl)amido)uranium(III) 以 苯 为溶剂， 以68%的产率得到1,4,7-tris(3-tert-butyl-5-(1-adamantyl)-2-hydroxybenzyl)-1,4,7-triazacyclononane uranium(III)
  参考文献：
  名称：

  Charge-Separation in Uranium Diazomethane Complexes Leading to C−H Activation and Chemical Transformation

  摘要：

  The reaction of diphenyldiazomethane with [(((t-Bu)ArO)(3)tacn)U(III)] (1) results in an eta(2)-bound diphenyldiazomethane uranium complex. This complex exhibits unusual electronic properties as a charge-separated species with a radical anionic open-shell ligand, [(((t-Bu)ArO)(3)tacn)U(IV)(eta(2)-NNCPh(2))] (2). Treating Ph(2)CN(2) with a uranium complex that contains a sterically more demanding adamantane functionalized ligand, [(((Ad)ArO)(3)tacn)U(III)] (3) results in an unprecedented C-H activation and nitrogen insertion to produce a five-membered heterocyclic indazole complex, [(((Ad)ArO)(3)tacn)U(IV)(eta(2)-3-phen(Ind))] (5). X-ray crystallography and spectroscopic characterization of these two compounds show that the [(((t-Bu)ArO)(3)tacn)U(IV)(eta(2)-NNCPh(2))] compound is a U(IV) complex with a radical anionic ligand, whereas [(((Ad)ArO)(3)tacn)U(IV)(eta(2)-3-phen(Ind))] is a U(IV) f(2) species with a closed-shell ligand.

  DOI：

  10.1021/ja0766472

文献信息

• Synthesis and Characterization of N-Heterocyclic Carbene Complexes of Uranium(III)
  作者：Hidetaka Nakai、Xile Hu、Lev N. Zakharov、Arnold L. Rheingold、Karsten Meyer

  DOI：10.1021/ic035142j

  日期：2004.2.1

  Reaction of [(((Ad)ArO)(3)tacn)U(III)] (1) or [((Me(3)Si)(2)N)(3)U(III)] (3) with tetramethylimidazol-2-ylidene (Me(4)IMC:) yields novel N-heterocyclic carbene complexes [((Ad ArO)(3)tacn)U(III)(Me(4)IMC:)] (2) and [((Me(3)Si)(2)N)(3)U(III)(Me(4)IMC:)] (4). Uranium complexes 2 and 4 represent the first examples of compounds with an N-heterocyclic carbene ligand coordinated to a low-valent uranium center. The paramagnetic complexes 1, 2, and 4 were characterized by (1)H NMR, UV-vis-NIR, and EPR spectroscopy as well as SQUID magnetization measurements and X-ray diffraction analyses. DFT studies indicate a significant degree of pi-bonding in the U(III)-carbene entity.