trans-PdII(Cl)2([1,1'-biphenyl-2-yl]diethylphosphine)2 | 1159848-02-8

• 英文名称: trans-PdII(Cl)2([1,1'-biphenyl-2-yl]diethylphosphine)2
• 英文别名: trans-Pd^II(Cl)₂([1,1'-biphenyl-2-yl]diethylphosphine)₂；trans-Pd^II(Cl)₂(EtJPhos)₂；trans-dichlorobis[diethyl(o-phenylphenyl)phosphane]palladium(II)
• CAS: 1159848-02-8
• 化学式: C₃₂H₃₈Cl₂P₂Pd
• 分子量: 661.927
• InChiKey: HTEPYZBDYUQISJ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  2-溴联苯 在 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 3.0h， 生成 trans-PdII(Cl)2([1,1'-biphenyl-2-yl]diethylphosphine)2
  参考文献：
  名称：

  Steric and Electronic Influences of Buchwald-Type Alkyl-JohnPhos Ligands

  摘要：

  The electron-donating and steric properties of Buchwald-type ligands ([1,1'-biphenyl-2-yl]dialkylphosphine; R-JohnPhos, where R = Me, Et, Pr-i, Cy, Bu-t) were determined. The pi-acidity and sigma-donating properties of the R-JohnPhos ligands were quantified using a Cotton-Kraihanzel analysis of the Cr-0(CO)(5)(R-JohnPhos) complexes. Somewhat surprisingly, the sigma-donating abilities of the R-JohnPhos ligands follow the trend Bu-t-JohnPhos < Et-JohnPhos < Pr-i-JohnPhos < Cy-JohnPhos << Me-JohnPhos. This ordering is proposed to arise from competition between the intrinsic electron-donating ability of the R groups (Me < Et < Pr-i approximate to Cy < Bu-t) and steric interactions (front and back strain) that decrease the electron-donating ability of the phosphine. X-ray crystallographic data of 22 metal complexes (general forms: trans-Cr-0(CO)(4)(PR3)(2), Pd-0(PR3)(2)(eta(2)-dba), and trans-Pd-II(Cl)(2)(PR3)(2)) were also analyzed to help explain the electronic trends measured for the R-JohnPhos ligands. The R-JohnPhos ligands are exceptionally sensitive to back strain in comparison to typical phosphines, and the strong sigma-donating ability of the Methyl-JohnPhos ligand is attributed to its ability to avoid both front strain and back strain. Consequently, the -PMe2 moiety allows for very short phosphorus-metal bond distances. Because of the sterically dominating o-biphenyl and close phosphorus-metal bond distances, MeJPhos maintains a large overall steric profile that is actually larger than that of CyJPhos as measured by percent buried volume (%V-bur). Overall, the -PMe2 moiety is a powerful way to incorporate strong sigma-donation into designer phosphines while retaining other advantageous structural and reactivity properties.

  DOI：

  10.1021/acs.inorgchem.5b02996

文献信息

• Palladium‐Catalyzed Suzuki–Miyaura Cross‐Coupling of Various Aryl Halides Using <i>ortho</i> ‐Alkyl‐Substituted Arylphosphanes and ( <i>ortho</i> ‐Alkylphenyl)alkylphosphanes under Microwave Heating
  作者：Sauli Vuoti、Juho Autio、Minna Laitila、Matti Haukka、Jouni Pursiainen

  DOI：10.1002/ejic.200700705

  日期：2008.1

  AbstractMono‐ and dinuclear palladium(II) chloride complexes of various ortho‐alkyl‐substituted aryl‐ and alkylphosphanes were prepared. Subsequently, these were characterized by 1H NMR and 31P1H} NMR spectroscopy, X‐ray crystallographic studies and mass spectroscopy. The palladium complexes were screened as potential catalysts for the microwave‐assisted Suzuki–Miyaura coupling reaction of several aryl halides under aerobic conditions. A preliminary study showed that excellent results can be obtained even for electron‐rich bromides and unactivated aryl chlorides with an optimized solvent, base and catalyst loading using specific phosphane ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Effective new palladium catalysts for the Suzuki coupling of various haloxylenes to prepare sterically hindered bi- and triaryls
  作者：Sauli Vuoti、Juho Autio、M. Haukka、J. Pursiainen

  DOI：10.1016/j.ica.2009.06.032

  日期：2009.10

  Several new ortho-alkyl and heteroalkyl substituted aryl and aryl alkyl phosphanes and their palladium complexes have been selectively prepared, characterized and compared as potential catalysts for the Suzuki coupling reaction. The modification of the structures of the palladium complexes were made in search of the best possible catalytic activity. The novel catalysts were subsequently used to synthesize sterically hindered bi- and triaryls by coupling various bulky, unactivated bromoxylenes and chloroxylenes with a range of phenyl boronic acids under microwave irradiation. We showed that under optimized reaction conditions, very good results can be obtained with a selection of the new phosphanes and their mononuclear palladium complexes. (C) 2009 Elsevier B. V. All rights reserved.