[(tmeda)Pd(C₆H₄-4-F)I] | 198825-76-2

• 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: [(tmeda)Pd(C₆H₄-4-F)I]
• 英文别名: fluorobenzene;palladium(2+);N,N,N',N'-tetramethylethane-1,2-diamine;iodide
• CAS: 198825-76-2
• 化学式: C₁₂H₂₀FIN₂Pd
• 分子量: 444.627
• InChiKey: BJJVWECFKVJOLO-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.26
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [(tmeda)Pd(C₆H₄-4-F)I] 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 生成
  参考文献：
  名称：

  Pd−X Bond Homolysis Dissociation Free Energy (BDFE) Scales of [(tmeda)Pd(4‐F−C ₆ H ₄ )X] (X=OR, NHAr) in DMSO

  摘要：

  AbstractTransition metal intermediates bearing M−X σ‐bonds are ubiquitous in metal‐mediated C−X bond transformations. Thermodynamic knowledge of M−X bond cleavage is crucial to explore relevant reactions; but little was accumulated till present due to lack of suitable determination methods. We here report the first systematic study of the Pd−X bond homolysis dissociation free energies [BDFE(Pd−X)] of representative [(tmeda)Pd(4‐F−C6H4)X] (tmeda=N,N,N′,N′‐tetramethylethylenediamine, X=OR or NHAr) in DMSO on the basis of reliable measurement of their bond heterolysis energies (ΔGhet(Pd−X)). Despite ΔGhet(Pd−O)s of palladium‐phenoxides are generally found about 8 kcal/mol smaller than ΔGhet(Pd−N)s of palladium‐amidos, their BDFE(Pd−X)s are observed comparable. The structure‐property relationship was investigated to disclose an enhancement effect of electron‐withdrawing groups on BDFE(Pd−X)s. Linear free energy relationship analysis revealed that Pd−X bonds are more sensitive than X−H bonds to structural variation. The energetic propensity of reductive elimination from arylpalladium complexes was evaluated by combinatorial use of BDFE(Pd−X)s and BDFE(C−X)s, indicating an overall thermodynamic bias to C−N bond formation.

  DOI：

  10.1002/ejic.202200556
• 作为产物：
  描述：

  四甲基乙二胺 、 对氟碘苯 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 以 甲苯 为溶剂， 以77 %的产率得到[(tmeda)Pd(C₆H₄-4-F)I]
  参考文献：
  名称：

  Pd−X Bond Homolysis Dissociation Free Energy (BDFE) Scales of [(tmeda)Pd(4‐F−C ₆ H ₄ )X] (X=OR, NHAr) in DMSO

  摘要：

  AbstractTransition metal intermediates bearing M−X σ‐bonds are ubiquitous in metal‐mediated C−X bond transformations. Thermodynamic knowledge of M−X bond cleavage is crucial to explore relevant reactions; but little was accumulated till present due to lack of suitable determination methods. We here report the first systematic study of the Pd−X bond homolysis dissociation free energies [BDFE(Pd−X)] of representative [(tmeda)Pd(4‐F−C6H4)X] (tmeda=N,N,N′,N′‐tetramethylethylenediamine, X=OR or NHAr) in DMSO on the basis of reliable measurement of their bond heterolysis energies (ΔGhet(Pd−X)). Despite ΔGhet(Pd−O)s of palladium‐phenoxides are generally found about 8 kcal/mol smaller than ΔGhet(Pd−N)s of palladium‐amidos, their BDFE(Pd−X)s are observed comparable. The structure‐property relationship was investigated to disclose an enhancement effect of electron‐withdrawing groups on BDFE(Pd−X)s. Linear free energy relationship analysis revealed that Pd−X bonds are more sensitive than X−H bonds to structural variation. The energetic propensity of reductive elimination from arylpalladium complexes was evaluated by combinatorial use of BDFE(Pd−X)s and BDFE(C−X)s, indicating an overall thermodynamic bias to C−N bond formation.

  DOI：

  10.1002/ejic.202200556

文献信息

• Bonding Energetics of Palladium Amido/Aryloxide Complexes in DMSO: Implications for Palladium‐Mediated Aniline Activation
  作者：Jun‐Yan Wu、Zhen Li、Jin‐Dong Yang、Jin‐Pei Cheng

  DOI：10.1002/anie.202011313

  日期：2020.12.21

  ΔGhet(Pd−O) values and of 14.5–19.5 kcal mol−1 for ΔGhet(Pd−N) values, respectively, implying a facile heterolytic detachment of the Pd ligands. Structure‐reactivity analyses of a modeling Pd‐mediated X−H bond activation reveal that the M−X bond metathesis is dominated by differences of the X−H and Pd−X bond strengths, the former being more influential. The ΔGhet(Pd−X) and pKa(X−H) parameters enable regulation

  金属-配体（ML）σ-键强度的热力学知识对于理解金属介导的转变至关重要。在这里，我们[[tmeda] PdArX]（tmeda = N，N，N ' ）提出了一种确定DMSO中Pd-X（X = OR和NHAr）键杂合能（ΔG het（Pd-X））的方法。，N'-四甲基乙二胺）作为模型络合物。该Δ ģ HET（PD-X）秤跨越范围2.6-9.0千卡摩尔-1为Δ G ^ HET（PD-O）的值和14.5-19.5千卡摩尔-1为Δ G ^ HET（Pd-N）值分别表示Pd配体的容易杂化分离。建模的Pd介导的X-H键活化的结构反应性分析表明，MX键的复分解作用主要受X-H和Pd-X键强度的差异影响，前者的影响更大。该Δ ģ HET（PD-X）和p ķ一个（X-H）参数使反应热力学和化学选择性的调节和诊断苯胺活化用Pd-X配合物的概率。
• Preparation and Properties of <i>trans</i>-Pd(Ar)(C⋮CPh)(PEt₃)₂. Intermolecular Alkynyl Ligand Transfer between Copper(I) and Palladium(II) Complexes Relevant to Palladium Complex Catalyzed Cross-Coupling of Terminal Alkyne with Haloarene in the Presence of CuI Cocatalyst
  作者：Kohtaro Osakada、Reiko Sakata、Takakazu Yamamoto

  DOI：10.1021/om970266n

  日期：1997.11.1

  trans-Pd(C6H4Me-p)(I)(PEt3)2 (2a) reacts with [Cu(C⋮CPh)(PPh3)]4 (Pd:Cu = 1:1) at room temperature to give the cross-coupling product PhC⋮CC6H4Me-p (3a) in 74% yield. Reactions of 2a with [Cu(C⋮CPh)(PPh3)]4 at −30 °C as well as of trans-Pd(C6H4X-p)(I)(PEt3)2 (2a, X = Me; 2b, X = OMe; 2c, X = F) with the alkynylcopper complex and additional PPh3 (2 mol/mol of Cu) at room temperature give mixtures of

  在室温下，反式-Pd（C 6 H 4 Me- p）（I）（PEt 3）2（2a）与[Cu（C⋮CPh）（PPh 3）] 4（Pd：Cu = 1：1）反应得到产率为74％的交叉偶联产物PhC⋮CC 6 H 4 Me- p（3a）。在-30°C下2a与[Cu（C⋮CPh）（PPh 3）] 4以及反式-Pd（C 6 H 4 X- p）（I）（PEt 3）2（2a）的反应，X =我; 2b，X = OMe; 2c，X ＝ F）与炔铜配合物和在室温下的另外的PPh 3（2mol / mol的Cu）得到PhC⋮CC 6 H 4 X- p的混合物（3a，X ＝ Me；3b，X ＝ OMe；H，H）。在图3c中，X ＝ F）和反式-Pd（C 6 H 4 X- p）（C⋮CPh）（PEt 3）2（4a，X ＝ Me；4b，X ＝ OMe；4c，X ＝ F）。配合物4a，b已从后面的反应混合物中分离出苯并已充
• Synthesis and Bond Activation Chemistry of Palladium(II) Pincer Complexes with a Weakly Coordinating Side Arm
  作者：A. P. Prakasham、Arkadi Vigalok、Andrei N. Vedernikov

  DOI：10.1021/acs.organomet.1c00710

  日期：2022.3.14

  the nature of the aromatic group at the Pd center. The ability to influence these interactions by changing the electron density at the metal was demonstrated in the stoichiometric Sonogashira-type cross-coupling reactions between the Pd complexes and phenylacetylene, which proceed via a reversible aromatization/dearomatization of the pincer ligand. Complexes with the electron-poor CF3 group showed

  已经制备了一系列带有弱配位苯并呋喃侧臂的 PNO 型钳形配体的 Pd(II) 芳基配合物。晶体学研究表明，Pd-O 距离非常长，超过 2.3 Å，这明显长于具有外环氧供体的结构相似的 PNO-Pd 配合物中的 Pd-O 距离。含给电子 (OMe) 和吸电子 (CF 3 ) 的配合物的晶体学和19 F NMR 溶液研究) 苯并呋喃氧原子对位的取代基揭示了 Pd-O 相互作用对 Pd 中心芳族基团性质的依赖性。通过改变金属上的电子密度来影响这些相互作用的能力在 Pd 配合物和苯乙炔之间的化学计量 Sonogashira 型交叉偶联反应中得到了证明，该反应通过钳形配体的可逆芳构化/脱芳构化进行。与它们的电子中性或富电子类似物相比，具有贫电子CF 3基团的配合物表现出更高的反应性。这些系统的 DFT 研究为观察到的反应模式的起源提供了进一步的机制洞察。
• Catalytic and stoichiometric reactions of Arylpalladium(II) complexes bearing a trans-chelating dinitrogen ligand with arylboronic acids
  作者：Yuji Suzaki、Takashi Saito、Kohtaro Osakada

  DOI：10.1016/j.jorganchem.2019.121088

  日期：2020.3

  Pd(II) complexes with 1,2-bis(2′-pyridylethylnyl)benzene (bpeb) ligand, PdCl2(bpep) and Pd(OAc)2(bpep), catalyze cross-coupling of arylboronic acids and aryl iodide, in spite of the trans-chelation of the ligand. Arylpalladium iodo and trifluoroacetate complexes with bpep ligand, Pd(C6H4X-4)(I)(bpep) (3a-3h, X = OMe, Me, H, COMe, CHO, COOEt, NO2, F), Pd(C6H3F2-2,4)(I)(bpep) (3i), Pd(C6H4X-4)(OCOCF3)(bpep)

  具有1,2-双（2'-吡啶基乙炔基）苯（bpeb）配体，PdCl 2（bpep）和Pd（OAc）2（bpep）的Pd（II）络合物催化芳基硼酸和芳基碘的交叉偶联尽管配体反式螯合。具有bpep配体Pd（C 6 H 4 X-4）（I）（bpep）的芳基碘钯和三氟乙酸盐络合物（3a-3h，X = OMe，Me，H，COMe，CHO，COOEt，NO 2，F）， Pd（C 6 H 3 F 2 -2,4）（I）（bpep）（3i），Pd（C 6 H 4 X-4）（OCOCF 3）（bpep）（4a-4e，X = OMe，Me ，H，COMe，CHO）和Pd（C通过具有tmeda配体（tmeda ＝N，N，N ′，N′-四甲基乙二胺）的Pd络合物的配体交换获得了 6 F 5）（OCOCF 3）（bpep）（4j）。芳基钯（II）三氟乙酸盐络合物Pd（C 6 H 4 OMe-4）（OCOCF 3）（bp
• Palladium-Assisted Room-Temperature Nucleophilic Substitution of an Unactivated Aryl Fluoride
  作者：Adam Scharf、Israel Goldberg、Arkadi Vigalok

  DOI：10.1021/om201175d

  日期：2012.2.27

  An organometallic palladium(II) complex of an 8-fluoroquinoline-based chelating ligand undergoes very facile nucleophilic substitution of the “unactivated” fluorine atom with the methoxy group upon simple stirring of its THF solution with sodium methoxide at room temperature. The final product of this reaction lacks the aromaticity in the heterocyclic ring of the quinoline moiety which might play an

  当在室温下简单地将其THF溶液与甲醇钠搅拌时，基于8-氟喹啉的螯合配体的有机金属钯（II）络合物会很容易地用甲氧基对“未活化”氟原子进行非常容易的亲核取代。该反应的最终产物在喹啉部分的杂环中缺乏芳香性，这可能在整个反应性中起重要作用。