(triethylphosphine)3RhPh | 170380-50-4

• 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: (triethylphosphine)3RhPh
• 英文别名: (PEt3)3RhPh
• CAS: 170380-50-4
• 化学式: C₂₄H₅₀P₃Rh
• 分子量: 534.488
• InChiKey: DTLVACYDQGYHQV-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：

  (triethylphosphine)3RhPh 、 3,3’,5,5’-四三氟甲基二苯甲酮 以 全氘代环己烷 为溶剂， 生成 [(Et3P)3Rh(3,5-(CF3)2C6H3)]
  参考文献：
  名称：

  将酮和腈插入有机铑（I）配合物中，并从铑（I）烷氧基和亚氨基配合物中消除β-烃基

  摘要：

  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

  DOI：

  10.1021/om800378v
• 作为产物：
  描述：

  [Rh(triethylphosphine)3(1,1-diphenylethanolato)] 在 P(C₂H₅)3 作用下， 以 氘代苯 为溶剂， 以61%的产率得到(triethylphosphine)3RhPh
  参考文献：
  名称：

  Direct Observation of β-Aryl Eliminations from Rh(I) Alkoxides

  摘要：

  beta-Aryl eliminations from a series of rhodium(I) alkoxides to form rhodium aryl complexes and free ketones are reported. Tertiary phenylmethoxide complexes [Rh(PEt3)n(OCPhRR')] (n = 2, 3) were prepared via alcoholysis of {Rh(PEt3)2[N(SiMe3)2} by the corresponding alcohols HOCPhRR' in the presence and absence of added PEt3. Heating of these complexes in the presence of added PEt3 generated the rhodium phenyl complex, (PEt3)3RhPh, and the corresponding ketones in good to high yields. Kinetic results are most consistent with irreversible beta-phenyl elimination from a bisphosphine-ligated rhodium alkoxide complex. Such bisphosphine complexes result from ligand dissociation from the trisphosphine complexes and have been isolated in some cases. The bisphosphine complexes are stabilized by Rh-Cphenyl interactions, as evidenced by an X-ray structure, and this structure with a metal-aryl interaction likely illustrates the pathway for C-C bond cleavage.

  DOI：

  10.1021/ja058550q

文献信息

• 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。
• Directly Observed Transmetalation from Boron to Rhodium. β-Aryl Elimination from Rh(I) Arylboronates and Diarylborinates
  作者：Pinjing Zhao、Christopher D. Incarvito、John F. Hartwig

  DOI：10.1021/ja068587q

  日期：2007.2.1

  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.
• Directly Observed Oxidative Addition of a Strong Carbon-Carbon Bond to a Soluble Metal Complex
  作者：Shyh-Yeon Liou、Michael Gozin、David Milstein

  DOI：10.1021/ja00143a028

  日期：1995.9