1,4,7-tris(3,5-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane | 180971-48-6

• 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(3,5-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane
• 英文别名: 1,4,7-tris(3,5-di-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane；2-[[4,7-Bis[(3,5-ditert-butyl-2-hydroxyphenyl)methyl]-1,4,7-triazonan-1-yl]methyl]-4,6-ditert-butylphenol
• CAS: 180971-48-6
• 化学式: C₅₁H₈₁N₃O₃
• 分子量: 784.222
• InChiKey: HPVOUTCWTDHNFD-UHFFFAOYSA-N

物化性质

• 沸点：
  732.3±55.0 °C(Predicted)
• 密度：
  1.027±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  13.6
• 重原子数：
  57
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  70.4
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tris(bis(trimethylsilyl)amido)europium(III) 、 1,4,7-tris(3,5-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane 以 四氢呋喃 为溶剂， 生成 Eu(1,4,7-tris(3,5-di-tert-butyl-2-oxybenzyl)-1,4,7-triazacyclononane)
  参考文献：
  名称：

  在锥型镧系元素络合物中捕获气态SO2：f元素化学中SO2的意外配位模式

  摘要：

  轻而易举：制备了镧系元素的第一分子SO 2配合物（Ln = Sm，Eu）。这些化合物可以可逆地配位气态SO 2。伴随着SO 2的添加和去除，配合物的颜色可逆地改变（参见方案）。SO 2化合物的结构可以在溶液和固态下确定。

  DOI：

  10.1002/anie.201109109
• 作为产物：
  描述：

  聚合甲醛 、 2,4-二叔丁基苯酚 、 1,4,7-三氮杂环壬烷 在 盐酸 作用下， 以 甲醇 为溶剂， 以50%的产率得到1,4,7-tris(3,5-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane
  参考文献：
  名称：

  镓，scan，铁和锰的苯氧基自由基配合物。

  摘要：

  六齿大环配体1,4,7-三（3,5-二甲基-2-羟基苄基）-1,4,7-三氮杂环壬烷（L CH 3H3），1,4,7-三（3,5-二-叔丁基-2-羟基苄基）-1,4,7-三氮杂环壬烷（L（Bu）H3）和1,4,7-三（3-叔丁基-5-甲氧基-2-羟基苄基）-1,4 ，7-三氮杂环壬烷（L OCH 3-H3）与三价（或四价）金属离子（Ga（III），Sc（III），Fe（III），Mn（III）， Mn（IV））。已合成以下配合物：[L（Bu）M]，其中M = Ga（1），Sc（2），Fe（3）；[L（Bu）Mn（IV）] PF6（4'）; [L OCH 3M]，其中M = Ga（1 a），Sc（2 a），Fe（3 a）；[L OCH 3Mn（IV）] PF 6（4a′）； [M + H] +。[L CH 3M]，其中M = Sc（2 b），Fe（3 b），Mn（III）（4 b）；[L CH

  DOI：

  10.1002/chem.19970030221

文献信息

• Metal- <i>versus</i> Ligand-Centered Oxidations in Phenolato−Vanadium and −Cobalt Complexes:  Characterization of Phenoxyl−Cobalt(III) Species
  作者：Achim Sokolowski、Britta Adam、Thomas Weyhermüller、Akihiro Kikuchi、Knut Hildenbrand、Robert Schnepf、Peter Hildebrandt、Eckhard Bill、Karl Wieghardt

  DOI：10.1021/ic970256e

  日期：1997.8.1

  synthesized: [L(Me)V(III)] (1), [L(Me)V(IV)]PF(6) (2), [(L(Me)H)V(V)(O)]PF(6) (3), [L(Bu)V(IV)]PF(6) (4), [L(OCH)()3V(IV)]PF(6) (5), [L(Me)Co(III)] (6), [L(Bu)Co(III)] (7), [L(OCH)()3Co(III)] (8). In addition, two complexes containing the L(Pr)Co(III) fragment have been prepared: [L(Pr)Co(III)(acac)](ClO(4)) (9) and [L(Pr)Co(III)(Cl(4)cat)].CH(3)CN (10), where acac(-) represents the ligand pentane-2,4-dionate

  侧臂大环1,4,7-三（3,5-二甲基-2-羟基苄基）-1,4,7-三氮杂环壬烷的配位化学，L（Me）H（3），1,4,7 -三（3,5-二叔丁基-2-羟基苄基）-1,4,7-三氮杂环壬烷，L（Bu）H（3），1,4,7-三（3-叔丁基-5） -甲氧基-2-羟基苄基）-1,4,7-三氮杂环壬烷，L（OCH）（）3H（3）和托曼配体1,4-二异丙基-7-（3,5-二叔丁基-2 -羟基苄基）-1,4,7-三氮杂环壬烷L（Pr）H与钒和钴（III）的关系已得到研究。已合成以下包含fac-N（3）O（3）供体的配合物：[L（Me）V（III）]（1），[L（Me）V（IV）] PF（6）（ 2），[（L（Me）H）V（V）（O）] PF（6）（3），[L（Bu）V（IV）] PF（6）（4），[L（OCH） （）3V（IV）] PF（6）（5），[L（Me）Co（III）]（6），[L（Bu）Co（III）]（7），[L（OCH）（）
• Uranium Tris-aryloxide Derivatives Supported by Triazacyclononane:  Engendering a Reactive Uranium(III) Center with a Single Pocket for Reactivity
  作者：Ingrid Castro-Rodriguez、Kristian Olsen、Peter Gantzel、Karsten Meyer

  DOI：10.1021/ja028342n

  日期：2003.4.1

  The synthesis and spectroscopic characterization of the mononuclear uranium complex [((ArO)(3)tacn)U(III)(NCCH(3))] is reported. The uranium(III) complex reacts with organic azides to yield uranium(IV) azido as well as uranium(V) imido complexes, [((ArO)(3)tacn)U(IV)(N(3))] and [((ArO)(3)tacn)U(V)(NSi(CH(3))(3))]. Single-crystal X-ray diffraction, spectroscopic, and computational studies of this analogous

  报道了单核铀复合物 [((ArO)(3)tacn)U(III)(NCCH(3))] 的合成和光谱表征。铀 (III) 配合物与有机叠氮化物反应生成铀 (IV) 叠氮化物以及铀 (V) 亚胺配合物 [((ArO)(3)tacn)U(IV)(N(3))] 和 [ ((ArO)(3)tacn)U(V)(NSi(CH(3))(3))]。描述了由三氮杂环壬烷支持的这种类似系列的铀三芳基氧化物配合物的单晶 X 射线衍射、光谱和计算研究。六齿、三阴离子配体以前所未有的方式与大铀离子配位，产生配位不饱和和高反应性的铀中心。大环三氮杂环壬烷三芳基氧化物衍生物占据六个配位点，三个芳基氧化物悬臂在金属中心形成一个三角平面。应用 DFT 量子力学方法来合理化反应性并阐明新合成化合物的电子结构。结果表明，深颜色的铀 (III) 和铀 (V) 物种通过 pi 键合相互作用稳定，分别涉及铀 f 轨道和轴向乙腈和亚胺配体。相比之下，无色铀
• Uranium complexes supported by an aryloxide functionalised triazacyclononane macrocycle: synthesis and characterisation of a six-coordinate U(iii) species and insights into its reactivityElectronic supplementary information (ESI) available: synthetic and analytical results, including elemental analysis, for all new complexes, crystallographic information for 2 and 3, and computational details for 1, figures and tables. See http://www.rsc.org/suppdata/cc/b2/b208473b/
  作者：Ingrid Castro-Rodriguez、Kristian Olsen、Peter Gantzel、Karsten Meyer

  DOI：10.1039/b208473b

  日期：2002.11.18

  A reactive low-valent uranium(III) complex supported by an aryloxide functionalised triazacyclononane has been synthesised and provides a platform for enhanced uranium reactivity.

  已合成了一种由芳氧官能化三氮杂环壬烷支持的活性低价铀（III）络合物，为增强铀的活性提供了平台。
• Phenoxyl Radical Complexes of Zinc(II)
  作者：Achim Sokolowski、Jochen Müller、Thomas Weyhermüller、Robert Schnepf、Peter Hildebrandt、Knut Hildenbrand、Eberhard Bothe、Karl Wieghardt

  DOI：10.1021/ja970417d

  日期：1997.9.1

  A series of phenoxyl radical complexes of zinc(II) have been generated in solution and, in one instance, isolated as solid material (5) in order to study their spectroscopic features by EPR, resonance Raman, and UV-vis spectroscopy. They serve as model complexes for the active form of the copper containing fungal enzyme galactose oxidase. The complexes [Zn((LH2)-H-1)]BF4 . H2O (1), [Zn((LH2)-H-2)]BF4 . H2O (2), [Zn((LH)-H-2)] (2a), [Zn(L-3)(Ph(2)acac)] (3), [Zn(L-4)(Ph(2)acac)] (4), and [Zn(L-4)(Me-acac)] (6) were synthesized from solutions of Zn(BF4)(2) . 4H(2)O and the corresponding ligand ((LH3)-H-1=1,4,7-tris(3,5-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclonane; (LH3)-H-2=1,4,7-tris(3-tert-butyl-5-methoxy-2-hydroxybenzyl)-1,4,7-triazacyclonane; (LH)-H-3=1,4-dimethyl-7-(3,5-di-tert-butyl-2-hydroxybenzyl)-1,4,7-triazacyclononane; (LH)-H-4=1,4-dimethyl-7-(3-tert-butyl-5-methoxy-2-hydroxybenzyl)-1,4,7-triazacyclononane, Ph(2)acac(-)=1,3-diphenyl-1,3-propanedionate, and Me-acac(-)=3-methyl-2,4-pentanedionate). Complexes 2, 3.0.5 toluene.1n-hexane, and 4 were structurally characterized by single-crystal X-ray crystallography. An electrochemical investigation of these complexes in CH3CN and/or CH2Cl2 solution revealed that the coordinated phenolate ligands undergo reversible one-electron oxidations with formation of coordinated phenoxyl radicals. Synthetically, the microcrystalline, paramagnetic (mu(eff)=1.7 mu(B)), solid material of [Zn(L-4)(Ph(2)acac)]PF6 (5) was produced by one electron oxidation of 4 by 1 equiv of ferrocenium hexafluorophosphate in dry CH2Cl2. Oxidation of coordinated phenol pendent arms in 1, 2, and 2a occurs at significantly higher potentials and is irreversible. Electronic (UV-vis), electron paramagnetic resonance (EPR), and resonance Raman (RR) spectra of the radicals have been studied in solution and allow the description of the electronic structure of these coordinated phenoxyl radical complexes.
• Charge-Separation in Uranium Diazomethane Complexes Leading to C−H Activation and Chemical Transformation
  作者：Oanh P. Lam、Patrick L. Feng、Frank W. Heinemann、Joseph M. O'Connor、Karsten Meyer

  DOI：10.1021/ja0766472

  日期：2008.3.1

  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.