[(Et3P)3Rh(p-anisyl)] | 864542-35-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: [(Et3P)3Rh(p-anisyl)]
• CAS: 864542-35-8
• 化学式: C₂₅H₅₂OP₃Rh
• 分子量: 564.514
• InChiKey: GDVOAXLCOGKGBS-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：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  以 not given 为溶剂， 生成 [(Et3P)3Rh(p-anisyl)]
  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

文献信息

• Insertions of Ketones and Nitriles into Organorhodium(I) Complexes and β-Hydrocarbyl Eliminations from Rhodium(I) Alkoxo and Iminyl Complexes
  作者：Pinjing Zhao、John F. Hartwig

  DOI：10.1021/om800378v

  日期：2008.9.22

  electron-poor aryl group. Independent preparation of 3f−g and studies on their thermal decomposition with added PEt3 confirmed that selective β-aryl elimination occurs to generate aryl complex 1g and the corresponding ketones. Analogous β-aryl eliminations from bis-phosphine rhodium(I) alkoxo complexes 3a−e and trisphosphine rhodium(I) alkoxo complexes 4b−e were also studied, and the kinetic results were most

  制备了一系列的三（三乙基膦）-连接的有机铑（I）配合物，并研究了它们与电子贫芳基腈和二芳基酮的反应。[（PEt 3）3 Rh（Ar）]（Ar =苯基（1a）或邻-茴香基（1e））与过量的电子贫芳基Ar'C≡N（Ar'= p -CF 3 C 6 H 4或3,5-bis（CF 3）C 6 H 3）形成Rh（I）亚氨基络合物（PEt 3）3 Rh [N═C（Ar）（Ar'）]}（2h - j） 。相反，3,5-bis（CF 3）C 6 H 3 CN没有插入芳基铑（I）配合物[（PEt 3）3 Rh（Ar）]（Ar = p -CF 3 C 6 H 4（1f）或3， 5-双（CF 3）C 6 H 3（1g）），含有更多的贫电子芳基。腈插入的动力学数据与涉及初始配体解离，随后经典的迁移插入的途径最一致。亚胺基络合物2i - j在较高温度下通过β-芳基消除而分解，同时电子侧差的芳基3,5-双（CF 3）C
• β-Aryl Eliminations from Rh(I) Iminyl Complexes
  作者：Pinjing Zhao、John F. Hartwig

  DOI：10.1021/ja054132+

  日期：2005.8.24

  β-Aryl eliminations from a series of iminyl complexes to form rhodium aryl complexes and free nitriles are reported. Iminyl complexes [Rh(PEt3)3(NCArAr‘)] were prepared from [Rh(COE)Cl]2, PEt3, LiN(SiMe3)2, and the imines HNCArAr‘. One example of these complexes was characterized by X-ray diffraction. Heating of these complexes in cyclohexane generated the rhodium aryl complexes and free nitriles in

  据报道，β-芳基从一系列亚胺基配合物中消除，形成铑芳基配合物和游离腈。亚胺基配合物 [Rh(PEt3)3(NCArAr')] 由 [Rh(COE)Cl]2、PEt3、LiN(SiMe3)2 和亚胺 HNCArAr' 制备。这些配合物的一个例子是通过 X 射线衍射表征的。在环己烷中加热这些配合物以高产率生成铑芳基配合物和游离腈；在苯中加热形成相同的产物，但产率略低。研究了在亚胺上具有不同芳基的配合物以评估芳基的迁移能力。邻茴香基的迁移比苯基的迁移快得多；苯基的迁移比富含电子的对茴香基的迁移速度稍快；苯基的迁移比受阻更大的邻甲苯基的迁移稍快。动力学研究表明，该反应在加入的膦和零氧浓度方面呈逆一级反应。