[Pd(C6H4CH2NMe2-κC,N)(NCMe)2]PF6 | 658063-62-8

• 英文名称: [Pd(C6H4CH2NMe2-κC,N)(NCMe)2]PF6
• CAS: 658063-62-8
• 化学式: C₁₃H₁₈N₃Pd*F₆P
• 分子量: 467.69
• InChiKey: DKFKMXVYGSKFEU-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：

  [Pd(C6H4CH2NMe2-κC,N)(NCMe)2]PF6 、 苯丙炔酸乙酯 以 二氯甲烷 为溶剂， 以93%的产率得到[Pd(C(Ph)=C(CO2Et)C6H4CH2NMe2-κC,N)(NCMe)2]PF6
  参考文献：
  名称：

  Insertion reactions of unsymmetrical ester-activated alkynes with o-benzylamine palladacycles: a regioselectivity study

  摘要：

  The regioselectivities of the insertion reactions of RCdropCCO(2)Et (R = Ph, CF3) into the aryl-palladium bond of several five-membered. ortho-palladated dimethylbenzylamine complexes, [PdCl(C6H4CH2NMe2-kappaC,N)](2) (1), [PdCl(C6H4CH2NMe2-kappaC,N)(L)] [L=PEt3 (2), DMPP (3)], [Pd(C6H4CH2NMe2-kappaC,N)(NCMe)(L)]PF6 [L=MeCN (4), PEt3 (9), DMPP (5)], [Pd(OSO2CF3)(C6H4CH2NMe2-kappaC,N)(DMPP)] (6), [Pd(C6H4CHNMe2-kappaC,N)(solvent)]PF6 (7) and [Pd(C6H4CH2NMe2-kappaC,N)(DMPP)(solvent)]PF6 (8), have been compared with the help of multinuclear NMR spectroscopy. In general, the carboxylate group in the resulting seven-membered palladacycles is preferentially located next to the phenyl group of the benzylamine moiety, but this substitution pattern can be reversed by use of complexes containing electron-deficient and/or coordinatively-unsaturated palladium centres. A mechanism, based both on the experimental results described in this paper and on DFT computations, is proposed. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00149-x
• 作为产物：
  描述：

  六氟磷酸银 、 bis[(benzyldimethylamino)chloropalladium(II)] 、 乙腈 以 乙腈 为溶剂， 生成 [Pd(C6H4CH2NMe2-κC,N)(NCMe)2]PF6
  参考文献：
  名称：

  Insertion reactions of unsymmetrical ester-activated alkynes with o-benzylamine palladacycles: a regioselectivity study

  摘要：

  The regioselectivities of the insertion reactions of RCdropCCO(2)Et (R = Ph, CF3) into the aryl-palladium bond of several five-membered. ortho-palladated dimethylbenzylamine complexes, [PdCl(C6H4CH2NMe2-kappaC,N)](2) (1), [PdCl(C6H4CH2NMe2-kappaC,N)(L)] [L=PEt3 (2), DMPP (3)], [Pd(C6H4CH2NMe2-kappaC,N)(NCMe)(L)]PF6 [L=MeCN (4), PEt3 (9), DMPP (5)], [Pd(OSO2CF3)(C6H4CH2NMe2-kappaC,N)(DMPP)] (6), [Pd(C6H4CHNMe2-kappaC,N)(solvent)]PF6 (7) and [Pd(C6H4CH2NMe2-kappaC,N)(DMPP)(solvent)]PF6 (8), have been compared with the help of multinuclear NMR spectroscopy. In general, the carboxylate group in the resulting seven-membered palladacycles is preferentially located next to the phenyl group of the benzylamine moiety, but this substitution pattern can be reversed by use of complexes containing electron-deficient and/or coordinatively-unsaturated palladium centres. A mechanism, based both on the experimental results described in this paper and on DFT computations, is proposed. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00149-x

文献信息

• A new chiral metalladiphosphine for early–late chemistry. Crystal structure of a D-camphor-based zirconium enolato phosphine and rearrangement of heterobimetallic Zr/Pd complexes †
  作者：Chris Mattheis、Pierre Braunstein、Axel Fischer

  DOI：10.1039/b008227i

  日期：——

  (dmba = o-C6H4CH2NMe2) or [PdCl2(SEt2)2] led to complete transfer of the functional ligand to the Pd(II) centre, with formation of [(dmba)Pd(PPh2C10H14O)] 6 or cis-[Pd(PPh2C10H14O)2] 8 and [Cp2ZrCl2]/[Cp2TiCl2], respectively. A heterobimetallic Zr/Pd intermediate complex 10 of this rearrangement could be detected. Complexes 6 and 8 were prepared independently by reaction of 1 with [Pd(dmba)(μ-Cl)]2 or [Pd(SEt2)2Cl2]

  双（phosphinoenolato）锆2，从膦樟脑衍生物制备3-外型-PPh 2 Ç 10 ħ 15 Ô 1，表示第一Ç 2含有的早过渡金属中心-对称手性二膦系在膦基通过一个enolato连锁。它可以选择性地组装路易斯酸-酸早期-晚期双金属组合，例如Zr / Cu和Zr / Ag配合物4和5。还制备了单膦烯醇式钛茂3。2或3的反应与[Pd（dmba）（μ-Cl）] 2（dmba =  o -C 6 H 4 CH 2 NMe 2）或[PdCl 2（SEt 2）2 ]导致官能团的完全转移配体到Pd（II）中心，形成[[dmba）Pd（PPh 2 C 10 H 14 O ）] 6或顺式-[ Pd（PPh 2 C 10 H 14 O ）2 ] 8和[Cp 2 ZrCl 2 ] / [Cp 2 TiCl 2 ]。可以检测到这种重排的异双金属Zr / Pd中间配合物10。配合物6和8是通过1的反应独
• The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT
  作者：Milan R. Milovanović、Mélanie Boucher、Yann Cornaton、Snežana D. Zarić、Michel Pfeffer、Jean‐Pierre Djukic

  DOI：10.1002/ejic.202100750

  日期：2021.12.7

  Enthalpies of reactions of alkynes with a palladacycle determined by isotherm titration calorimetry in chlorobenzene reveal major solvation-related discrepancies with a standard continuum solvation-DFT approach.

  在氯苯中通过等温线滴定量热法测定的炔烃与钯环的反应焓揭示了与标准连续溶剂化-DFT 方法的主要溶剂化相关差异。