[Pd(di-tert-butylbipyridine)2(acetate)2] | 1251918-28-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [Pd(di-tert-butylbipyridine)2(acetate)2]
• 英文别名: [Pd(II)(4,4’-di-tert-butyl-2,2’-dipyridyl)(OAc₂)]；(4,4′-di-tert-butyl-2,2′-bipyridine)Pd^II(OAc)；[Pd(tBu₂bpy)(OAc)₂]；Pd(OAc)₂(tBu₂bpy)；(dtbpy)Pd^II(OAc)
• CAS: 1251918-28-1
• 化学式: C₂₂H₃₀N₂O₄Pd
• 分子量: 492.911
• InChiKey: IVHIAIUSBJZBJJ-UHFFFAOYSA-L

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(di-tert-butylbipyridine)2(acetate)2] 、 4-(3,4-二羟基苯基)苯-1,2-二醇 以 四氢呋喃 为溶剂， 反应 2.0h， 以38%的产率得到
  参考文献：
  名称：

  新系列双核 Pd(II) Biscatecholato 配合物的合成和表征：基于非纯配体的混合价配合物近红外吸收变化范围广泛的方法

  摘要：

  在这项研究中，我们报告了一系列新的混合价 (MV) 配合物的合成，这些配合物的间隔电荷转移 (IVCT) 能量从第一个到第三个电信窗口可变......

  DOI：

  10.1246/bcsj.20180187
• 作为产物：
  描述：

  palladium diacetate 、 4,4'-二叔丁基-2,2'-二吡啶 在 溶剂黄146 作用下， 以 丙酮 为溶剂， 反应 18.0h， 以82%的产率得到[Pd(di-tert-butylbipyridine)2(acetate)2]
  参考文献：
  名称：

  银盐在钯催化的芳烃和杂芳烃CH官能化反应中的作用

  摘要：

  Silver carboxylate salts are widely used as additives in palladium-catalyzed C-H functionalization reactions. However, the role of these silver additives is often not fully understood. This paper describes an investigation of the role of AgOPiv in the stoichiometric activation of C6F5H at a well-defined Pd-II complex as well as in the Pd-II-catalyzed oxidative dimerization of 2-alkylthiophenes. Both in situ NMR spectroscopy and H/D exchange studies of the reactions of C6F5H implicate a role for AgOPiv in the C-H cleavage event, generating Ag-C6F5 as an intermediate. The catalytic studies show similar trends despite the different conditions and substrates, suggesting that AgOPiv promotes a similar metalation of the thiophene in the catalytic transformations. This proposal is supported by DFT calculations, which show energetically feasible pathways for concerted metalation-deprotonation of both 2-methylthiophene and pentafluorobenzene at [Ag(OPiv)](2). These studies suggest that initial metalation of C-H substrates at Ag-I carboxylates should be considered as a plausible pathway in C-H functionalization reactions involving mixtures of Ag and Pd salts.

  DOI：

  10.1021/acs.organomet.6b00437
• 作为试剂：
  描述：

  2-甲基噻吩 在 [Pd(di-tert-butylbipyridine)2(acetate)2] 、 特戊酸银 作用下， 以 1,4-二氧六环 为溶剂， 反应 18.0h， 生成 5,5-二甲基-2,2-并噻吩
  参考文献：
  名称：

  银盐在钯催化的芳烃和杂芳烃CH官能化反应中的作用

  摘要：

  Silver carboxylate salts are widely used as additives in palladium-catalyzed C-H functionalization reactions. However, the role of these silver additives is often not fully understood. This paper describes an investigation of the role of AgOPiv in the stoichiometric activation of C6F5H at a well-defined Pd-II complex as well as in the Pd-II-catalyzed oxidative dimerization of 2-alkylthiophenes. Both in situ NMR spectroscopy and H/D exchange studies of the reactions of C6F5H implicate a role for AgOPiv in the C-H cleavage event, generating Ag-C6F5 as an intermediate. The catalytic studies show similar trends despite the different conditions and substrates, suggesting that AgOPiv promotes a similar metalation of the thiophene in the catalytic transformations. This proposal is supported by DFT calculations, which show energetically feasible pathways for concerted metalation-deprotonation of both 2-methylthiophene and pentafluorobenzene at [Ag(OPiv)](2). These studies suggest that initial metalation of C-H substrates at Ag-I carboxylates should be considered as a plausible pathway in C-H functionalization reactions involving mixtures of Ag and Pd salts.

  DOI：

  10.1021/acs.organomet.6b00437

文献信息

• Formation of Ethane from Mono-Methyl Palladium(II) Complexes
  作者：Monica D. Lotz、Matthew S. Remy、David B. Lao、Alireza Ariafard、Brian F. Yates、Allan J. Canty、James M. Mayer、Melanie S. Sanford

  DOI：10.1021/ja412338k

  日期：2014.6.11

  This article describes the high-yielding and selective oxidatively induced formation of ethane from mono-methyl palladium complexes. Mechanistic details of this reaction have been explored via both experiment and computation. On the basis of these studies, a mechanism involving methyl group transmetalation between Pd(II) and Pd(IV) interediates is proposed.

  本文描述了从单甲基钯配合物高产率和选择性氧化诱导的乙烷形成。该反应的机理细节已经通过实验和计算进行了探索。在这些研究的基础上，提出了一种涉及 Pd(II) 和 Pd(IV) 中间体之间甲基转移的机制。
• New π-extended catecholato complexes of Pt(<scp>ii</scp>) and Pd(<scp>ii</scp>) containing a benzothienobenzothiophene (BTBT) moiety: synthesis, electrochemical behavior and charge transfer properties
  作者：Keishiro Tahara、Yuya Ashihara、Toshiki Higashino、Yoshiki Ozawa、Tomofumi Kadoya、Kunihisa Sugimoto、Akira Ueda、Hatsumi Mori、Masaaki Abe

  DOI：10.1039/c8dt05057k

  日期：——

  synthesis of metal complexes involving a BTBT moiety, which was achieved by complexation of 2,2′-bipyridyl complexes of Pt(II) and Pd(II) with dihydroxy-substituted BTBT (1) as a new π-extended catecholato ligand (tBu2Bpy = 4,4′-di-tert-butyl-2,2′-dipyridyl). The resulting complexes M(tBu2Bpy)(O2BTBT) (M = Pt (3Pt) and Pd (3Pd)) were characterized by UV–vis spectroscopy, density functional theory (DFT) calculations

  苯并噻吩并苯并噻吩（BTBT）及其衍生物作为有机场效应晶体管材料和分子导体受到越来越多的关注。该报告介绍了涉及BTBT部分的金属配合物的首次合成，该合成是通过将Pt（II）和Pd（II）的2,2'-联吡啶配合物与作为新的π-的二羟基取代的BTBT（1）配合而实现的。扩展的儿茶酚配体（t Bu 2 Bpy = 4,4'-二叔丁基-2,2'-二吡啶基）。将得到的配合物M（吨卜2 BPY）（O 2 BTBT）（M =的Pt（3点）和Pd（3PD））通过紫外可见光谱，密度泛函理论（DFT）计算和循环伏安法进行表征。在包含两个氧取代基并随后进行金属配位后，BTBT的给电子能力大大增强。这使的化学氧化3点和3PD与单电子氧化状态的温和的化学氧化剂（二茂铁鎓六氟磷酸盐）和形成。虽然3点和第三方开发表现出源自邻苯二酚→Bpy配体到配体的电荷转移跃迁的吸收带，是此类儿茶酚络合物的典型特征，自由基阳离子表现出独特的π–π
• Oxidation of a Cyclometalated Pd(II) Dimer with “CF₃⁺”: Formation and Reactivity of a Catalytically Competent Monomeric Pd(IV) Aquo Complex
  作者：Yingda Ye、Nicholas D. Ball、Jeff W. Kampf、Melanie S. Sanford

  DOI：10.1021/ja107780w

  日期：2010.10.20

  The reaction of [(bzq)Pd(OAc)](2) (bzq = benzo[h]quinoline) with "CF3+" reagents to afford the monomeric Pd-IV aquo complex (bzq)Pd(CF3)(OAc)(2)(OH2) is demonstrated. Heating this Pd-IV adduct at 60 degrees C for 12 h leads to highly chemoselective aryl-CF3 bond-forming reductive elimination. The rate and yield of this transformation are both significantly enhanced by the addition of Bronsted and Lewis acidic additives. The mechanism of C-CF3 bond formation from (bzq)Pd(CF3)(OAc)(2)(OH2) has been studied, and the major pathway is proposed to involve pre-equilibrium acetate dissociation followed by C-CF3 coupling. Finally, this monomeric Pd-IV complex is shown to be a kinetically competent intermediate for C-H trifluoromethylation with "CF3+" reagents. Collectively, these studies provide valuable insights about the speciation, nuclearity, and reactivity of Pd intermediates in catalytic C-H trifluoromethylation reactions.