(PEt3)2RhN(SiMe3)2 | 864361-15-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (PEt3)2RhN(SiMe3)2
• 英文别名: (triethylphosphine)2Rh[N(SiMe3)2]；(Rh(PEt3)2[N(SiMe3)2])；(PEt3)2Rh[N(SiMe3)2]
• CAS: 864361-15-9
• 化学式: C₁₈H₄₈NP₂RhSi₂
• 分子量: 499.61
• InChiKey: VXKVRXRMOSDXDT-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：
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• 环数：
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• 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

• 作为反应物：
  描述：

  (PEt3)2RhN(SiMe3)2 以99%的产率得到
  参考文献：
  名称：

  末端烷氧基配体和配位烯烃之间的碳-氧键形成。烯烃插入铑醇盐的证据

  摘要：

  报道了一系列通过分子内烯烃配位稳定的双（膦）铑（I）醇盐的制备和反应性。{Rh(PEt3)2[kappa1:eta2-OCRR'(CH2)nCH=CH2]} (n = 1, 2) 通过 {Rh(PEt3)2[N(SiMe3)2]} 的醇解制备醇 HOCRR'(CH2)nCH=CH2。原位生成的 {Rh(PEt3)2[kappa1:eta2-OCRR'(CH2)2CH=CH2]} 在环境温度下不稳定，在添加的 PEt3 存在下分解，得到 2,2-二取代-5-亚甲基四氢呋喃和 [(PEt3)4Rh-H] 的产率很高。动力学和氘标记结果支持通过将烯烃直接插入 Rh-O 键，然后快速消除 β-氢化物来实现合成氧化途径。相比之下，{Rh(PEt3)2[kappa1:eta2-OCRR'CH2CH=CH2]}被分离为稳定的晶体，并且Rh-烯烃相互作用由X-射线结构证明。这些复合物的加热产生 [Rh(PEt3)2(eta2-allyl)]

  DOI：

  10.1021/ja063347w

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
• Direct Observation of β-Aryl Eliminations from Rh(I) Alkoxides
  作者：Pinjing Zhao、Christopher D. Incarvito、John F. Hartwig

  DOI：10.1021/ja058550q

  日期：2006.3.1

  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.
• 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.