(dtbpe)Rh-OTf | 1573125-06-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (dtbpe)Rh-OTf
• 英文别名: (1,2-bis(di-tert-butylphosphino)ethane)Rh-OTf
• CAS: 1573125-06-0
• 化学式: C₁₉H₄₀F₃O₃P₂RhS
• 分子量: 570.439
• InChiKey: MZOBARLOMRZMCE-UHFFFAOYSA-M

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：

  (dtbpe)Rh-OTf 、 苯 在 三氟甲磺酸三甲基硅酯 作用下， 反应 6.0h， 以74%的产率得到[(1,2-bis(di-tert-butylphosphino)ethane)Rh(μ6-C6H6)][OTf]
  参考文献：
  名称：

  Synthesis and Reactivity of Three-Coordinate (dtbpe)Rh Silylamides: CO₂ Bond Cleavage by a Rhodium(I) Disilylamide

  摘要：

  Rhodium(I) silylamide complexes supported by the 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) ligand have been prepared and their structures and reactivity studied. Although the complexes degrade over time to release the corresponding silylamines, they react cleanly with silver(I) salts to transfer the amido group at ambient temperature. The bis(trimethylsilyl)amide complex (dtbpe)Rh-N(TMS)(2) reacts with CO2 to form a carbamate complex that decomposes via loss of hexamethyldisiloxane to form a bis(mu-isocyanate) dimer, suggesting that silylamides may be useful nitrene-group and nitrogen-atom sources through selective N-Si bond cleavage.

  DOI：

  10.1021/om401130q
• 作为产物：
  描述：

  [(1,2-bis(di-tert-butylphosphino)ethane)Rh(μ-Cl)]2 以 四氢呋喃 、 苯 为溶剂， 反应 12.08h， 生成 (dtbpe)Rh-OTf
  参考文献：
  名称：

  Synthesis and Reactivity of Three-Coordinate (dtbpe)Rh Silylamides: CO₂ Bond Cleavage by a Rhodium(I) Disilylamide

  摘要：

  Rhodium(I) silylamide complexes supported by the 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) ligand have been prepared and their structures and reactivity studied. Although the complexes degrade over time to release the corresponding silylamines, they react cleanly with silver(I) salts to transfer the amido group at ambient temperature. The bis(trimethylsilyl)amide complex (dtbpe)Rh-N(TMS)(2) reacts with CO2 to form a carbamate complex that decomposes via loss of hexamethyldisiloxane to form a bis(mu-isocyanate) dimer, suggesting that silylamides may be useful nitrene-group and nitrogen-atom sources through selective N-Si bond cleavage.

  DOI：

  10.1021/om401130q

文献信息

• Chalcogen Extrusion from Heteroallenes and Carbon Monoxide by a Three-Coordinate Rh(I) Disilylamide
  作者：Matthew T. Whited、Lisa Qiu、Alex J. Kosanovich、Daron E. Janzen

  DOI：10.1021/acs.inorgchem.5b00305

  日期：2015.4.6

  We report the reactions of several heteroallenes (carbon disulfide, carbonyl sulfide, and phenyl isocyanate) and carbon monoxide with a three-coordinate, bis(phosphine)-supported Rh(I) disilylamide (1). Carbon disulfide reacts with 1 to afford a silyltrithiocarbonate complex similar to an intermediate previously invoked in the deoxygenation of CO2 by 1, and prolonged heating affords a structurally

  我们报告了几种杂三烯（二硫化碳，羰基硫和苯基异氰酸酯）和一氧化碳与三配位双（膦）负载的Rh（I）二甲硅烷基酰胺（1）的反应。与二硫化碳进行反应1，得到silyltrithiocarbonate复杂类似于CO的脱氧先前调用的中间2由1，和长时间加热，得到结构上不寻常的μ-κ 2（小号，小号'）：κ 2（小号，小号' ）-三硫代碳酸酯二聚体。羰基硫与1反应以提供结构独特的Rh（SCNCS）金属环，该化合物衍生自两次插入的OCS和N-to-O甲硅烷基迁移。异氰酸苯基酯与1反应生成二聚双（苯基氰基氨基）桥联的复合物，该复合物是由多个甲硅烷基基团迁移和氮-氧交换所产生的，类似于先前在二氧化碳中观察到的反应性。1的能力通过甲硅烷基基团迁移来激活碳-硫族元素的多键还得到了其与一氧化碳的反应性的支持，在该反应中，六甲基二硅氧烷被驱逐时还可以观察到氮对氧的复分解反应。对于所有报道的反应，在合适的条件下都可以