pyridinium.tetrakis(pentafluorophenyl)borate | 146874-32-0

• 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: pyridinium.tetrakis(pentafluorophenyl)borate
• 英文别名: Pyridin-1-ium;tetrakis(2,3,4,5,6-pentafluorophenyl)boranuide
• CAS: 146874-32-0
• 化学式: C₅H₅N*C₂₄BF₂₀*H
• 分子量: 759.152
• InChiKey: ITHXDEKMLPVMDE-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  6.35
• 重原子数：
  51
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  14.1
• 氢给体数：
  1
• 氢受体数：
  21

反应信息

• 作为反应物：
  描述：

  pyridinium.tetrakis(pentafluorophenyl)borate 、 以 氘代四氢呋喃 为溶剂， 反应 144.0h， 生成
  参考文献：
  名称：

  氢加（钳）IrI（CO）配合物：立体和电子因素的重要性

  摘要：

  (POCOP)Ir-I(CO) [POCOP = kappa(3)-C6H3-2,6-(OPR2)(2) for R = Bu-t, Pr-i] and (PCP)Ir-I(CO) [PCP = kappa(3)-C6H3-2,6-(CH2PR2)(2) for R = Bu-t and Pr-i] complexes can add hydrogen via two distinct pathways. When R = Bu-t, (POCOP)Ir(CO) and (PCP)Ir(CO) complexes only add hydrogen via a proton-catalyzed pathway due to steric effects, yielding trans-dihydride complexes. For R = Pr-i, both systems oxidatively add hydrogen to give cis-dihydride complexes which thermally isomerize to more thermodynamically favorable trans-dihydride species, consistent with previous reports. Proton-catalyzed hydrogen addition pathways are also observed for both Pr-i-substituted (pincer)Ir(CO) complexes. (PCP)Ir(CO) complexes add hydrogen under milder conditions than the analogous POCOP species. Intermediate hydrido-pyridine Ir(III) carbonyl complexes from the proton-catalyzed pathway have been synthesized and characterized. This is the first report of a series of complexes shown to add hydrogen via concerted oxidative addition or a proton-catalyzed pathway to the same iridium center.

  DOI：

  10.1021/acs.organomet.6b00598

文献信息

• Cyclopentadienyl Complexes of Ir^III for Attempted C−D Bond Activation
  作者：Robert D. Robinson、Werner Kaminsky、Jeremiah J. Scepaniak

  DOI：10.1002/ejic.202300369

  日期：2023.9.25

  The complexes Cp(MeIm)IrI₂ and Cp^Me4(MeIm)IrCl₂ have been prepared and subsequently methylated to form Cp(MeIm)IrMe₂ and Cp^Me4(MeIm)IrMe₂ (Cp=η⁵‐C₅H₅, Cp^Me4=η⁵‐C₅HMe₄, MeIm=1,3‐dimethylimidazol‐2‐ylidene). We attempted unsuccessfully to use the dimethyl complexes to study C−D bond activation via methyl‐group abstraction. Protonation with one equivalent of a weak acid, such as 2,6‐dimethylpyridinium chloride, affords methane and Ir^III methyl chloride complexes. ¹H‐NMR experiments show addition of pyridinium [BArF₂₀]⁻ (BArF₂₀=[B(C₆F₅)₄]⁻) to the dimethyl species forms [Cp(MeIm)IrMe(py)]⁺[BArF₂₀]⁻ (py=pyridine) or [Cp^Me4(MeIm)IrMe(py)]⁺[BArF₂₀]⁻ respectively, alongside methane, while use of the [BArF₂₀]⁻ salts of more bulky 2,6‐dimethylpyridinium and 2,6‐di‐tert‐butylpyridinium gave an intractable mixture. Likewise, the generation of 16 e⁻ species [Cp^Me4(MeIm)IrMe]⁺[BArF₂₀]⁻ or [Cp(MeIm)IrMe]⁺[BarF₂₀]⁻ at low temperature using 2,6‐dimethylpyridinium or 2,6‐di‐tert‐butylpyridinium in thawing C₆D₆ or toluene‐d₈ formed an intractable mixture and did not lead to C−D bond activation. X‐ray structures of several Ir^III complexes show similar sterics as that found for the previously reported Cp* analogue.

  摘要制备了 Cp(MeIm)IrI2 和 CpMe4(MeIm)IrCl2 复合物，随后将其甲基化，形成 Cp(MeIm)IrMe2 和 CpMe4(MeIm)IrMe2 （Cp=η5-C5H5，CpMe4=η5-C5HMe4，MeIm=1,3-二甲基咪唑-2-亚基）。我们曾尝试用二甲基络合物来研究通过甲基基团萃取活化 C-D 键，但未成功。用一种等效的弱酸（如 2,6-二甲基氯化吡啶）进行质子化，可得到甲烷和 IrIII 甲基氯化物络合物。1H-NMR 实验显示，将吡啶鎓 [BArF20]- （BArF20=[B(C6F5)4]-）加入二甲基络合物后，分别形成 [Cp(MeIm)IrMe(py)]+[BArF20]-（py=吡啶）或 [CpMe4(MeIm)IrMe(py)]+[BArF20]-、而使用体积更大的 2,6-二甲基吡啶鎓和 2,6-二叔丁基吡啶鎓的[BArF20]-盐，则会产生难以处理的混合物。同样，在解冻的 C6D6 或甲苯-d8 中使用 2,6-二甲基吡啶鎓或 2,6-二叔丁基吡啶鎓在低温下生成 16 个 e- 物种 [CpMe4(MeIm)IrMe]+[BArF20]- 或 [Cp(MeIm)IrMe]+[BarF20]- 时，也会形成难溶混合物，并且不会导致 C-D 键活化。几种 IrIII 复合物的 X 射线结构显示出与先前报告的 Cp* 类似物类似的立体结构。
• Hydrogen Addition to (pincer)Ir^I(CO) Complexes: The Importance of Steric and Electronic Factors
  作者：Jonathan M. Goldberg、Sophia D. T. Cherry、Louise M. Guard、Werner Kaminsky、Karen I. Goldberg、D. Michael Heinekey

  DOI：10.1021/acs.organomet.6b00598

  日期：2016.10.24

  (POCOP)Ir-I(CO) [POCOP = kappa(3)-C6H3-2,6-(OPR2)(2) for R = Bu-t, Pr-i] and (PCP)Ir-I(CO) [PCP = kappa(3)-C6H3-2,6-(CH2PR2)(2) for R = Bu-t and Pr-i] complexes can add hydrogen via two distinct pathways. When R = Bu-t, (POCOP)Ir(CO) and (PCP)Ir(CO) complexes only add hydrogen via a proton-catalyzed pathway due to steric effects, yielding trans-dihydride complexes. For R = Pr-i, both systems oxidatively add hydrogen to give cis-dihydride complexes which thermally isomerize to more thermodynamically favorable trans-dihydride species, consistent with previous reports. Proton-catalyzed hydrogen addition pathways are also observed for both Pr-i-substituted (pincer)Ir(CO) complexes. (PCP)Ir(CO) complexes add hydrogen under milder conditions than the analogous POCOP species. Intermediate hydrido-pyridine Ir(III) carbonyl complexes from the proton-catalyzed pathway have been synthesized and characterized. This is the first report of a series of complexes shown to add hydrogen via concerted oxidative addition or a proton-catalyzed pathway to the same iridium center.