| 205697-86-5

• CAS: 205697-86-5
• 化学式: C₄₅H₅₅ClO₄Ti
• 分子量: 743.262
• InChiKey: MFNNJEMBUIVGCM-UHFFFAOYSA-J

计算性质

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

反应信息

• 作为产物：
  描述：

  [p-Bu(t)-calix[4]-(OMe)2(O)2TiCl2] * 1.36 toluene 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  杯[4]芳烃部分定义的羰基表面的钛碳官能团及其氧化还原化学

  摘要：

  摘要[p -Bu t -calix [4]-（OMe）2（OH）2]（1）的锂化反应，然后与TiCl 3（thf）3或TiCl 4（thf）2反应，生成相应的钛-calix [4]芳烃配合物[p -Bu t -calix [4]-（OMe）2（O）2] TiCl]（2）和[p -Bu t -calix [4]-（OMe）2（O ）2] TiCl 2]（3）。1与TiCl 4（thf）2的反应导致杯[4]芳烃脱甲基，并出现[p -Bu t -calix [4]-（OMe）2（O）3] TiCl]（4），其水解导致[p -Bu t -calix [4]-（OMe）（OH）3]（6）。6的制备可以一锅合成法进行。2和4均使用常规程序进行烷基化反应，从而形成了出乎意料的稳定有机金属物质，即[p -Bu t -calix [4]-（OMe）2（O）2 Ti（R）]（R = Me（7） ; CH 2 Ph（8），p

  DOI：

  10.1016/s0020-1693(97)05863-5

文献信息

• Periodic Trends in Highly Dispersed Groups IV and V Supported Metal Oxide Catalysts for Alkene Epoxidation with H₂O₂
  作者：Nicholas E. Thornburg、Anthony B. Thompson、Justin M. Notestein

  DOI：10.1021/acscatal.5b01105

  日期：2015.9.4

  Supported metal oxides are important catalysts for selective oxidation processes like alkene epoxidation with H2O2. The reactivity of these catalysts is dependent on both identity and oxide structure. The dependence of the latter on the synthesis method can confound attempts at comparative studies across the periodic table. Here, SiO2-supported metal oxide catalysts of Ti(IV), Zr(IV), Hf(IV), V(V), Nb(V)

  负载的金属氧化物是用于选择性氧化过程（例如用H 2 O 2进行烯烃环氧化）的重要催化剂。这些催化剂的反应性取决于同一性和氧化物结构。后者对合成方法的依赖可能会使整个元素周期表中比较研究的尝试混淆。在此，合成了Ti（IV），Zr（IV），Hf（IV），V（V），Nb（V）和Ta（V）（均为IV和V组）的SiO 2负载金属氧化物催化剂通过嫁接一系列相关的杯芳烃配位化合物，表面密度小于〜0.25 nm –2。通过固态NMR，紫外可见光和X射线吸收近边缘光谱学研究了精选的催化剂。在45和65°C下，检查合成后的煅烧材料对环己烯和苯乙烯（1.0 M）与H 2 O 2（0.10 M）的环氧化作用。Nb催化剂以高性能材料的形式出现，煅烧后的Nb-SiO 2的环己烯转化频率为2.4 min -1（比Ti-SiO 2快2倍），对直接（非自由基）环氧化途径的选择性为〜85％ 。与煅烧形式相比，合成后的Zr，H
• Structural Assessment and Catalytic Consequences of the Oxygen Coordination Environment in Grafted Ti−Calixarenes
  作者：Justin M. Notestein、Leandro R. Andrini、Vitaly I. Kalchenko、Felix G. Requejo、Alexander Katz、Enrique Iglesia

  DOI：10.1021/ja065830c

  日期：2007.2.1

  Calixarene-Ti complexes were grafted onto SiO2 (0.18-0.24 Ti nm(-2)) to form isolated and accessible Ti centers persistently coordinated to multidentate calixarene ligands. Grafted Ti-tert-butylcalix[4]arenes gave Ti K-edge absorption spectra with pre-edge features at 4968.6-4968.9 eV, independently of Ti surface density and of their use in epoxidation catalysis. The structure and reactivity of grafted Ti-calix[4]arenes were weakly dependent on thermal treatment below 573 K, and the relative epoxidation rates of trans- and cis-alkenes showed that calixarene ligands did not restrict access to Ti centers more than corresponding calcined Ti-SiO2 materials. For all materials, C-13 NMR and UV-visible spectroscopies confirmed the presence of Ti-O-Si connectivity and identical ligand-to-metal transitions. Grafted Ti-homooxacalix[3]arene complexes, however, gave weaker pre-edge features at higher energies (similar to 4969.5 eV), consistent with greater Ti 3d occupancy and coordination numbers greater than four, and 20-fold lower cyclohexene epoxidation rate constants (per Ti) than on calix[4]arene-based materials. These different rates and near-edge spectra result from aldehyde formation caused by unimolecular cleavage of ether linkages in homooxacalix[3]arene ligands during grafting, leading to higher coordination and electron density at Ti centers. Materials based on tert-butylcalix[4]arene and homooxacalix[3]arenes led to similar epoxidation rates and near-edge spectra after calcination, consistent with the conversion of both materials to isolated Ti centers with identical structure. These materials provide a systematic approach for relating oxidation reactivity to Ti 3d occupancy, a descriptor of Lewis acid strength, and Ti coordination, because they provide Ti centers with varying electron density and coordination, but maintain accessible active centers with uniform structure and unrestricted access to reactants.