(neocuproine)Pd(OAc)₂ | 152506-86-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: (neocuproine)Pd(OAc)₂
• 英文别名: (2,9-dimethyl-1,10-phenanthroline)-palladium(II) acetate；2,9-Dimethyl-1,10-phenanthroline;palladium(2+);diacetate
• CAS: 152506-86-0
• 化学式: C₁₈H₁₈N₂O₄Pd
• 分子量: 432.772
• InChiKey: LGPDFFBQCRBSGX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  0.91
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  106
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (neocuproine)Pd(OAc)₂ 、 三氟乙酸 以 甲醇 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  Synthesis and characterization of monochelated carboxylatopalladium(II) complexes with nitrogen-donor chelating ligands. Crystal structures of diacetato(1,10-phenanthroline)- and diacetato(2,9-dimethyl-1,10-phenanthroline)-palladium(II)

  摘要：

  Two series of monochelated carboxylatopalladium(II) complexes of general formula [Pd(L-L)(MeCO2)2] and [Pd(L-L)(CF3CO2)2] [L-L = 1,10-phenanthroline (phen), 2,2'-bipyridine and their substituted derivatives) have been prepared and characterized. The chemical behaviour of the complexes in solution has been studied in different solvents mainly by means of H-1 NMR experiments. These showed that, unlike the acetato complexes, the trifluoroacetato derivatives undergo partial dissociation of the anionic ligand in Me2SO solution at room temperature. A similar behaviour was also observed for the acetato complexes in CD3OD. The signals of the H-2, H-9 protons in the phenanthroline series, and those of H-6, H-6 in the bipyridine one, are excellent probes for the evaluation of the environment of the palladium atom. The crystal structures of [Pd(phen)(MeCO2)2], [Pd(2,9-dmphen)(MeCO2)2].0.40CH2Cl2 and [Pd(2,9-dmphen)(MeCO2)2].0.25CHCl3 (2,9-dmphen=2,9-dimethyl-1,10-phenanthroline) have been determined. The co-ordination geometry around palladium is square planar in all the structures, but significant deviations from the idealized geometry occur in the last two in order to relieve the interligand contacts. These monochelated carboxylatopalladium(II) complexes are active catalysts in carbon monoxide-olefin copolymerization. Some preliminary results on their catalytic activity are also reported.

  DOI：

  10.1039/dt9940001903
• 作为产物：
  描述：

  新铜试剂 、 palladium diacetate 以 丙酮 为溶剂， 以94%的产率得到(neocuproine)Pd(OAc)₂
  参考文献：
  名称：

  Well-defined palladium(ii) complexes for ligand-enabled C(sp³)-alkynylation

  摘要：

  报道了8-甲基喹啉配体促进的C(sp3)-炔基化的第一个例子。该反应由明确定义的Pd(II)配合物催化。目前的C(sp3)-炔基化具有广泛的底物范围以及对官能团的耐受性，并且在温和条件下进行。

  DOI：

  10.1039/c5dt02772a
• 作为试剂：
  描述：

  1,2-辛二醇 在 (neocuproine)Pd(OAc)₂ 、 2,6-二甲氧基-1,4-苯醌 、 tetrabutylammonium tetrafluoroborate 、 溶剂黄146 作用下， 以 二甲基亚砜 为溶剂， 反应 8.0h， 以85%的产率得到1-羟基辛烷-2-酮
  参考文献：
  名称：

  新铜pro钯催化剂介导邻二醇的电解

  摘要：

  合成电化学与可持续化学原理非常吻合，因此，它被认为是比目前某些合成方法更环保的方法。在这里，我们提出了一种对邻二醇的化学选择性氧化的新策略。新cuproine钯催化剂的集成和电合成。苯醌被用作有效的介体，因为还原的物质（氢醌）可以在电极表面相对较低的电势下容易地被再氧化。NeocuproinePd（OAc）2在室温下对邻二醇的电解反应中有效地充当催化剂。考虑到酒精的有氧氧化反应通常需要更复杂的催化剂，即[neocuproinePdOAc] 2，这是一项了不起的观察。[OTf] 2。在本文中，我们描述了新cuproinePd（OAc）2催化剂选择性氧化二醇的电解条件的优化。所提出的方法导致高产率的醇的转化，并且提供了一种有趣的替代方案，借助电化学在温和条件下进行氧化反应。

  DOI：

  10.1016/j.electacta.2017.07.044

文献信息

• Synthesis of 2-Alkynoates by Palladium(II)-Catalyzed Oxidative Carbonylation of Terminal Alkynes and Alcohols
  作者：Qun Cao、N. Louise Hughes、Mark J. Muldoon

  DOI：10.1002/chem.201602558

  日期：2016.8.16

  PdII catalyst, utilizing a simple and inexpensive amine ligand (TMEDA), allows 2‐alkynoates to be prepared in high yields by an oxidative carbonylation of terminal alkynes and alcohols. The catalyst system overcomes many of the limitations of previous palladium carbonylation catalysts. It has an increased substrate scope, avoids large excesses of alcohol substrate and uses a desirable solvent. The catalyst

  均相 Pd II催化剂利用简单且廉价的胺配体 (TMEDA)，可以通过末端炔烃和醇的氧化羰基化以高产率制备 2-炔酸酯。该催化剂体系克服了以往钯羰基化催化剂的许多局限性。它具有更大的底物范围，避免大量过量的醇底物并使用理想的溶剂。该催化剂采用氧气作为终端氧化剂，可以在更安全的气体混合物下运行。
• Synthesis, Structure, and Reactivity of the Novel Pentacoordinate Palladium Complex [Pd(Phen)₂(CO₂CH₃)](PF₆)
  作者：Rossella Garrone、Anna Maria Romano、Roberto Santi、Roberto Millini

  DOI：10.1021/om980315b

  日期：1998.9.1

  Reaction of [Pd(phen)(CO2CH3)2] (1) with phenanthrolinium hexafluorophosphate (2) gives in high yield the unprecedented pentacoordinate palladium complex [Pd(phen)2(COOMe)](PF6) (3) in which Pd displays a strongly distorted square pyramidal coordination. The reactivity of 3 toward bases was explored too.

  [Pd（phen）（CO 2 CH 3）2 ]（1）与菲咯啉六氟磷酸盐（2）的反应获得了高收率的前所未有的五配位钯络合物[Pd（phen）2（COOMe）]（PF 6）（3）其中Pd表现出强烈扭曲的方形锥体结构。还探讨了3对碱基的反应性。
• Selective catalytic oxidation of diglycerol
  作者：Huan Wang、Nam Duc Vu、Guo-Rong Chen、Estelle Métay、Nicolas Duguet、Marc Lemaire

  DOI：10.1039/d0gc03239e

  日期：——

  The selective oxidation of α,α-diglycerol was studied using oxygen as a clean oxidant in the presence of a palladium/neocuproine complex. After optimization of the reaction parameters, the mono-oxidation product was obtained with 93% NMR yield (up to 76% isolated yield). The product was named “diglycerose” considering that it mainly exists as a cyclic hemi-ketal form.

  研究了在钯/新古铜络合物存在下，使用氧气作为清洁氧化剂对α，α-甘油的选择性氧化的方法。优化反应参数后，以93％的NMR收率获得单氧化产物（分离出的收率高达76％）。考虑到该产品主要以环状半缩酮形式存在，故将其命名为“甘油二酸酯”。
• [EN] QUINOLINES AND PROCESS FOR THE PREPARATION THEREOF<br/>[FR] QUINOLINES ET PROCÉDÉ POUR LEUR PRÉPARATION
  申请人：COUNCIL SCIENT IND RES

  公开号：WO2016113759A1

  公开（公告）日：2016-07-21

  The present invention discloses novel N-Heterocyclic compounds of formula A, [Formula A] And a ligand-enabled palladium-catalyzed process for preparation of novel N-Heterocyclic compounds of Formula A via C-H alkynylation of N-heterocycles with alkynyl halides.

  本发明揭示了一种新的A式N-杂环化合物，[A式]以及一种配体催化的钯催化过程，通过N-杂环与炔基卤化物的C-H炔基化反应制备新的A式N-杂环化合物。
• Role of the Metal, Ligand, and Alkyl/Aryl Group in the Hydrolysis Reactions of Group 10 Organometallic Cations [(L)M(R)]⁺
  作者：Matthew J. Woolley、George N. Khairallah、Gabriel da Silva、Paul S. Donnelly、Brian F. Yates、Richard A. J. O’Hair

  DOI：10.1021/om400358q

  日期：2013.12.9

  level of theory. Two main types of primary product ions were observed: the aqua adduct [(L)M(R)(H2O)]+ (5) and the hydroxide [(L)M(OH)]+ (7), formed via a hydrolysis reaction. A secondary product ion, arising from formation of the adduct [(L)M(OH)(H2O)]+, was also observed when L = phen, R = CH3, and M = Pt. The rates of reaction of 4 and the product branching ratios for 5 and 7 were dependent upon the

  水与配位不饱和基团的反应中的有机金属10的阳离子[（L）M（R）] +（4 ;其中L = 1,10-菲咯啉（phen）的，新亚铜试剂（新）; M =镍，钯，铂; R = CH 3，C 6 H ^ 5，CH 2 C ^ 6 ħ 5），通过羧酸盐配合物的脱羧形成[（L）M（O 2 CR）] +，均在气相中使用的多级质量的组合检查M06 / SDD6-31 + G（d）理论水平的光谱实验和DFT计算。观察到两个主要类型的初级产物离子组成：AQUA加合物[（L）M（R）（H 2 O）] +（5）和氢氧化[（L）M（OH）] +（7），通过水解反应来形成。一种二次产物离子，从形成的加合物的产生[（L）M（OH）（H 2 O）] +，还观察到，当L =苯，R = CH 3，和M =铂。的反应速率4和产品分支比为5和7分别为依赖于的M，L的性质，和R.当L =啉和R = CH 3，氢氧化7个占优势为镍，