(PEt3)3Rh[OB(Mes)2] | 929547-92-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (PEt3)3Rh[OB(Mes)2]
• CAS: 929547-92-2
• 化学式: C₃₆H₆₇BOP₃Rh
• 分子量: 722.565
• InChiKey: UJCLMZIBGGWJHF-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：

  (PEt3)3Rh[OB(Mes)2] 以 全氘代环己烷 为溶剂， 以87%的产率得到[(PEt3)3Rh(Mes)]
  参考文献：
  名称：

  Directly Observed Transmetalation from Boron to Rhodium. β-Aryl Elimination from Rh(I) Arylboronates and Diarylborinates

  摘要：

  Transmetalation from boron to rhodium in the absence of basic activators is reported to proceed by beta-aryl elimination from a series of triethylphospine-ligated rhodium(I) arylboronates and diarylborinates. [Rh(PEt3)(3)OB(OH)Ar] were prepared by treating {Rh(PEt3)(2)[N(SiMe3)(2)} with the corresponding arylboronic acid, ArB(OH)(2), in the presence of added PEt3. One example of these complexes was characterized by X-ray diffraction. [Rh(PEt3)(3)OB(mesityl)(2)] and [Rh(PEt3)(2)OB(mesityl)(2)] were prepared by analogous methods from dimesitylborinic acid in the presence and absence of added PEt3. Heating of the trisphosphine boronate complexes in cyclohexane generated the rhodium aryl complexes, [(PEt3)(3)RhAr] and boroxin in good to high yields. [Rh(PEt3)(3)OB(mesityl)(2)] also underwent aryl migration to form [(PEt3)(3)Rh(mesityl)] and a cyclic boroxine. Kinetic studies showed that migration of more electron-poor aryl groups from the boronate complexes was slightly faster than migration of more electron-poor aryl groups and that migration of the o-anisyl group was particularly fast. Kinetic results are most consistent with a ligand dissociation pathway with a rate-limiting beta-aryl elimination from a 14-electron, bis(phosphine) intermediate.

  DOI：

  10.1021/ja068587q
• 作为产物：
  描述：

  (PEt3)2Rh[OB(Mes)2] 、 三乙基膦 以 not given 为溶剂， 以99%的产率得到(PEt3)3Rh[OB(Mes)2]
  参考文献：
  名称：

  Directly Observed Transmetalation from Boron to Rhodium. β-Aryl Elimination from Rh(I) Arylboronates and Diarylborinates

  摘要：

  Transmetalation from boron to rhodium in the absence of basic activators is reported to proceed by beta-aryl elimination from a series of triethylphospine-ligated rhodium(I) arylboronates and diarylborinates. [Rh(PEt3)(3)OB(OH)Ar] were prepared by treating {Rh(PEt3)(2)[N(SiMe3)(2)} with the corresponding arylboronic acid, ArB(OH)(2), in the presence of added PEt3. One example of these complexes was characterized by X-ray diffraction. [Rh(PEt3)(3)OB(mesityl)(2)] and [Rh(PEt3)(2)OB(mesityl)(2)] were prepared by analogous methods from dimesitylborinic acid in the presence and absence of added PEt3. Heating of the trisphosphine boronate complexes in cyclohexane generated the rhodium aryl complexes, [(PEt3)(3)RhAr] and boroxin in good to high yields. [Rh(PEt3)(3)OB(mesityl)(2)] also underwent aryl migration to form [(PEt3)(3)Rh(mesityl)] and a cyclic boroxine. Kinetic studies showed that migration of more electron-poor aryl groups from the boronate complexes was slightly faster than migration of more electron-poor aryl groups and that migration of the o-anisyl group was particularly fast. Kinetic results are most consistent with a ligand dissociation pathway with a rate-limiting beta-aryl elimination from a 14-electron, bis(phosphine) intermediate.

  DOI：

  10.1021/ja068587q