(η5-1,2-di-tert-butylcyclopentadienyl)tricarbonylrhenium | 175086-88-1

• 英文名称: (η5-1,2-di-tert-butylcyclopentadienyl)tricarbonylrhenium
• CAS: 175086-88-1
• 化学式: C₁₆H₂₁O₃Re
• 分子量: 447.548
• InChiKey: KBXSLMKKQMHTQC-UHFFFAOYSA-N

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

• 作为反应物：
  描述：

  叔丁基过氧化氢 、 (η5-1,2-di-tert-butylcyclopentadienyl)tricarbonylrhenium 以 癸烷 、 苯 为溶剂， 反应 0.42h， 以18%的产率得到C₁₃H₂₁O₃Re
  参考文献：
  名称：

  Synthesis of Cyclopentadienyl-Based Trioxo-rhenium Complexes and Their Use as Deoxydehydration Catalysts

  摘要：

  The cyclopentadienyl-based trioxo-rhenium complexes (CpReO3)-Re-ttt (Cp-ttt = 1,2,4-tritert-butylcyclopentadienyl) 1b and Cp*ReO3 (Cp* = pentamethylcyclopentadienyl) 4b) are known to be active catalysts for the deoxydehydration (DODH) of vicinal diols to olefins. Here, we report on the preparation of a series of complexes of the general formula Cp'ReO3 (Cp' = 1,3-di-tert-butylcyclopentadienyl (Cp-tt, 2b, 18%), 1,2,3-triisopropylcyclopentadienyl (3b, 4%), 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyl (6b, 36%), and tetramethylcyclopentadienyl (7b, 33%)) in which the electronic and steric properties of the Cp' ligand are varied. These complexes were synthesized via oxidative decarbonylation from the corresponding Cp'Re(CO)(3) complexes with either H2O2 or tBuOOH. An in situ NMR investigation revealed that complexes 2b, 3b, and 6b are unstable under the oxidizing reaction conditions. This information was used to determine the optimal reaction time to isolate the complexes 2b, 3b, and 6b. These piano-stool configurated Cp'ReO3 complexes were characterized spectroscopically and by single crystal X-ray diffraction. The new complexes 2b, 3b, 6b, and 7b were found to be generally less thermally stable than (CpReO3)-Re-ttt (1b) or Cp*ReO3 (4b). It appeared that 2b and 6b were better catalysts for the DODH of 1,2-octanediol to octene with PPh3 as an oxygen-atom acceptor. Remarkably, the less substituted Cp'ReO3 complexes (1b, 2b, and 3b) afforded significantly less 2-octene (presumably from isomerization of the primary 1-octene product) in comparison to those containing per-alkylated Cp-moieties (4b and 6b).

  DOI：

  10.1021/acs.organomet.6b00120
• 作为产物：
  描述：

  五羰基溴铼(I) 、 2,3-di-tert-butyl-5-trimethylstannyl-1,3-cyclopentadiene 以 四氢呋喃 为溶剂， 以17%的产率得到(η5-1,2-di-tert-butylcyclopentadienyl)tricarbonylrhenium
  参考文献：
  名称：

  用于将1,2-二叔丁基环戊二烯基配体转移到过渡金属的锡和transition试剂

  摘要：

  易于制备能够转移1，2-二叔丁基环戊二烯基部分的新的锡和th试剂，并将其用于促进该插入配体的过渡金属有机金属化学反应。1,2-二叔丁基环戊二烯锂（1）与SnClMe 3选择性清洁反应，得到2,3-二叔丁基-5-三甲基锡烷基-1,3-环戊二烯（2），然后与之反应的Re（CO）5溴，以形成半夹心络合物[RE（η 5 -C 5 H ^ 3（1,2-卜吨）2）（CO）3 ]（3）。乙醇th与1,5-二叔丁基-1,3-环戊二烯在己烷中的反应提供了优异的环戊二烯基转移试剂，1,2-二叔丁基环戊二烯化（（4）。用的[Ru（COD）Cl为基准的铊盐反应2 ] Ñ，得到夹心复合物的[Ru（η 5 -C 5 H ^ 3（1,2-卜2吨）2）]（5）。

  DOI：

  10.1016/0020-1693(95)04517-1