[RhCl(cyclooctene)]₂ | 74219-49-1

• 英文名称: [RhCl(cyclooctene)]₂
• 英文别名: [RhCl(coe)]₂
• CAS: 74219-49-1；40904-63-0
• 化学式: C₁₆H₂₈Cl₂Rh₂
• 分子量: 497.115
• InChiKey: XIAVAPHRLTUILR-JGMWHDQESA-L

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：

  [RhCl(cyclooctene)]₂ 、 diisopropylphosphine(diphenylphosphine)methane 以 甲苯 为溶剂， 以75%的产率得到
  参考文献：
  名称：

  Wolf, Justin; Manger, Matthias; Schmidt, Ulrich, Journal of the Chemical Society, Dalton Transactions

  摘要：

  DOI：
• 作为试剂：
  描述：

  一氧化碳 、 3-(allyloxy)-1-phenyl-2-propyne 在 [RhCl(cyclooctene)]₂ 作用下， 以 二丁醚 为溶剂， 反应 24.0h， 以41%的产率得到6-phenyl-3a,4-dihydro-1H-cyclopenta[c]furan-5(3H)-one
  参考文献：
  名称：

  整合CO2还原和后续羰基化：旨在扩展CO2的化学利用

  摘要：

  目前，尽管在该领域已经取得了巨大的进步，但是扩大CO 2的化学固定范围仍然是一个挑战。鉴于CO在无数工业羰基化方法中的广泛应用，提出了另一种策略，其中将CO 2还原为CO与羰基化与非原位生成的CO结合，从而有效地提供了药学和农业化学上有吸引力的分子。因此，CO 2在这项研究中，三氯硅烷在封闭的两室反应器中使用CsF到CO有效地还原了CO。随后，钯催化的氨基羰基化，芳基碘化物的羰基化Sonogashira偶联以及铑（I）介导的Pauson–Khand型反应顺利进行，分别产生了酰胺，炔酮和双环环戊烯酮。此外，形成的炔酮可进一步成功转化为一系列杂环，例如吡唑，3a-羟基异恶唑并[3,2 - a ]异吲哚-8-（3a H）-one衍生物和嘧啶类化合物。该协议的显着特征包括操作简便，效率高和相对广泛的应用范围，这代表了CO 2转化的替代途径。

  DOI：

  10.1002/cssc.201800902

文献信息

• Alkyl− and Aryl−Oxygen Bond Activation in Solution by Rhodium(I), Palladium(II), and Nickel(II). Transition-Metal-Based Selectivity
  作者：Milko E. van der Boom、Shyh-Yeon Liou、Yehoshoa Ben-David、Linda J. W. Shimon、David Milstein

  DOI：10.1021/ja9738889

  日期：1998.7.1

  Reaction of [RhCl(C8H14)(2)](2) (C8H14 = cyclooctene)with 2 equiv of the aryl methyl ether phosphine 1 in C6D6 results in an unprecedented metal insertion into the strong sp(2)-sp(3) aryl-O bond. This remarkable reaction proceeds even at room temperature and occurs directly, with no intermediacy of C-H activation or insertion into the adjacent weaker ArO-CH3 bond. Two new phenoxy complexes (8 and 9), which are analogous to the product of insertion into the ArO-CH3 bond (had it taken place) were prepared and shown not to be intermediates in the Ar-OCH3 bond cleavage process. Thus, aryl-O bond activation by the nucleophilic Rh(I) is kinetically preferred over activation of the alkyl-O bond. The phenoxy Rh(I)-eta(1)-N-2 complex (8) is in equilibrium with the crystallographically characterized Rh(I)-mu-N-2-Rh(I) dimer (12). Reaction of [RhCl(C8H14)(2)](2) With 2 equiv of the aryl methyl ether phosphine 2, PPh3, and excess HSiR3 (R = OCH2CH3, CH2CH3) results also in selective metal insertion into the aryl-O bond and formation of (CH3O)SiR3. Thus, transfer of a OCH3 group from carbon to silicon was accomplished, showing that hydrosilation of an unstrained aryl-O single bond by a primary silane is possible. The selectivity of C-O bond activation is markedly dependent on the transition-metal complex and the alkyl group involved, allowing direction of the C-O bond activation process at either the aryl-O or alkyl-O bond. Thus, contrary to the reactivity of the rhodium complex, reaction of NiI2 or Pd(CF3CO2)(2) with 1 equiv of 1 in ethanol or C6D6 at elevated temperatures results in exclusive activation of the sp(3)-sp(3) ArO-CH3 bond, while reaction of the analogous aryl ethyl ether 4 and Pd(CF3CO2)(2) results in both sp(3)-sp(3) and sp(2)-sp(3) C-O bond activation. The resulting phenoxy Pd(II) complex (18) is fully characterized by X-ray analysis. Heating the latter under mild dihydrogen pressure results in hydrodeoxygenation to afford an aryl-Pd(II) complex (19).