(CpMe4H)Re(CO)3 | 111405-95-9

• 英文名称: (CpMe4H)Re(CO)3
• 英文别名: tricarbonyl(η5-tetramethylcyclopentadienyl)rhenium；(CpMe₄H)Re(CO)₃
• CAS: 111405-95-9
• 化学式: C₁₂H₁₃O₃Re
• 分子量: 391.44
• InChiKey: KDOLWKLMWUPICF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (CpMe4H)Re(CO)3 、 双氧水 以 水 、 苯 为溶剂， 反应 1.0h， 以33%的产率得到
  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：

  十羰基二铼 、 1,2,3,4-四甲基-1,3-环戊二烯 反应 5.67h， 以98%的产率得到(CpMe4H)Re(CO)3
  参考文献：
  名称：

  环戊二烯基三羰基铼配合物的合成及环戊二烯基取代基的一些异常反应

  摘要：

  基于环戊二烯基的三羰基铼配合物 (Cp'Re(CO)3) 是相应的基于环戊二烯基的三氧铼配合物 (Cp'ReO3) 的方便前体，它们是二醇脱氧 (DODH) 成烯烃的潜在催化剂。为了评估不同Cp-取代基的影响，合成了一系列烷基取代的Cp'Re(CO)3配合物(1a-8a)。从 Re2(CO)10 与相应的 Cp'H 配体 (1-8) 的反应中获得了高产率 (86-98%)，其中 Cp 的给电子特性随着取代基的数量增加而增加。芳基取代的类似配合物 10a-12a 是通过 ReBr(CO)5 与去质子化配体 (Cp'Li) 的锂盐的盐复分解获得的，发现芳基会减少电子供体。此外，(CpMe4H)Re(CO)3 8a 与过量配体的不寻常的 [6+4] 环加成反应导致高度不对称的 Cp'Re(CO)3 配合物 9a。最后，四苯基环戊二烯酮配体与 Re2(CO)10 的反应导致分离出两种不寻常的化合物：Shvo

  DOI：

  10.1002/ejic.201601220