(η(4)-C44H52O4)Mo=O | 888953-45-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: (η(4)-C44H52O4)Mo=O
• CAS: 888953-45-5
• 化学式: C₄₄H₅₂MoO₅
• 分子量: 756.834
• InChiKey: WRZFEIZQLAWYHQ-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  10.8
• 重原子数：
  50.0
• 可旋转键数：
  0.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (η(4)-C44H52O4)Mo=O 、 二氯二氧化钼 、 caesium 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Molybdocalixarene结构通过边缘去质子化控制。杯[4]芳烃Mo（VI）一氧杂配合物和杯[4]芳烃碱金属/ Mo（VI）二氧杂配合物的合成，表征和晶体结构。

  摘要：

  我们报告了一系列的杯[4]亚芳基钼（VI）二氧杂配合物M2RC4MoO2（M =碱金属，R = H或Bu（t）），已通过NMR，X射线，IR，UV / vis和元素分析。可以通过下边缘去质子化，杯[4]芳烃的对位上的基团和碱金属抗衡离子来控制Molybdocalix [4]芳烃的结构。在下部边缘的单质子化会导致杯[4]芳烃Mo（VI）一元氧配合物RC4MoO（R = H，Bu（t）或烯丙基），完全的质子化会产生杯[4]芳烃Mo（VI）二氧杂复合体。结构研究表明，HC4 Mo（VI）二氧杂配合物容易通过阳离子-pi相互作用和不同杯芳烃单元之间的配位形成聚合物结构。但是，由于叔丁基在杯芳烃的对位上的空间位阻，Bu（t）C4 Mo（VI）二氧杂配合物趋于形成二聚体或四聚体。还原的副产物A和C的结构通过X射线衍射研究确定。杯芳烃单阴离子与MoO2Cl2反应形成RC4MoO的机理似乎包括在Mo = O键上添加杯芳烃-OH基。

  DOI：

  10.1021/ic060404d
• 作为产物：
  描述：

  Mo2(η(4)-C44H53O4)2 、 氧气 以 not given 为溶剂， 生成 (η(4)-C44H52O4)Mo=O
  参考文献：
  名称：

  Dinuclear Molybdenum and Tungsten Complexes with Metal−Metal Triple Bonds Supported by p-tert-Butylcalix[4]arene Ligands

  摘要：

  In hydrocarbon solvents the compounds M-2(NMe2)(6) (M = Mo, W) react with p-tert-butylcalix[4]arene, H4L, to give the complexes (H2NMe2)(2)[M-2(mu,eta(2),eta(2)-L)(2)], 1 (M = Mo, W). In the molecular structure of 1.4THF, the calix[4]arene ligands span the Mo=Mo bond of distance 2.193(1) Angstrom in a mu,eta(2),eta(2) manner such that each Mo atom is coordinated by four phenolic oxygen atoms that lie roughly in a plane with Mo-Mo-O angles that range from 92 to 102 degrees. The calix[4]arene bowl encapsulates the H2NMe2 cations tightly as judged by H-1 NMR spectroscopy, and heating to 100 degrees C under a dynamic vacuum in the solid state fails to remove HNMe2. However, upon refluxing in pyridine, compounds 1 are converted to (H2NMe2)(2)[M-2(eta(4)-L)(2)].xpy, 2.xpy. The molecule of 2.4py (M = Mo) has a center of symmetry, and the Mo-2-calix[4]arene unit has a dumbbell shape (Mo equivalent to Mo bond distance 2.226(1) Angstrom). Each Mo atom has four Mo-O phenoxide bonds, one of which is hydrogen-bonded to a H2NMe2 cation, which in turn is hydrogen-bonded to a pyridine molecule. Each calix[4]arene bowl encapsulates one molecule of pyridine. Heating compounds 2 under a dynamic vacuum at 100 degrees C for 3 days forms compounds 3 of formula M-2(eta(4)-HL)(2). A partial crystal structure determination of 3.xC(6)H(6) (M = Mo) revealed Mo equivalent to Mo bonds, 2.226(6) and 2.214(7) Angstrom, supported by eta(4)-HL ligands. Compounds 3 are formed directly in the reactions between M-2(O'Bu)(6) compounds and H4L in benzene at room temperature (1 or 2 days). Compounds 3 react in hydrocarbon solutions with HNMe2 to give the compounds (H2NMe2)(2)[M-2(eta(4)-L)(2)], 2. For tungsten, 3 and 2 react in benzene to give (H2NMe2)[W-2(eta(4)-L)(eta(4)-HL)], 4, which crystallizes with seven molecules of benzene, two of which are encapsulated in the calix[4]arene bowls. The W=W bond, 2.304(1) Angstrom, is spanned by one H2NMe2 cation that hydrogen-bonds to a pair of phenolic oxygen atoms while another pair of oxygen atoms in the trans position are directly hydrogen-bonded such that a short O...O distance results, 2.338(9) Angstrom. The monomethylated p-tert-butylcalix[4]arene, H3L(1), reacts with Mo-2(NMe2)(6) to give 3, HNMe2, and Me3N whereas Mo-2(O'Bu)(6) and H3L(1) yield Mo-2(eta(4)-L(1))(2), 5, and (BuOH)-Bu-t. The dimethylated p-tert-butylcalix[4]arene, H2L(2), failed to react with either Mo-2(NMe2)(6) or Mo-2((OBu)-Bu-t)(6) even under prolonged reflux. These results are discussed in terms of the mechanisms of substitution and isomerization reactions of M=M complexes and are compared with known reactions involving chelating biphenoxides and the coordination chemistry of calix[4]arene ligands.

  DOI：

  10.1021/ic990513a