Pd(2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N)(OCOMe) | 1306772-95-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: Pd(2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N)(OCOMe)
• CAS: 1306772-95-1
• 化学式: C₁₄H₁₇BrN₂O₄Pd
• 分子量: 463.624
• InChiKey: WQJUWQVSOVTERD-MOEKMLTRSA-M

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(2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N)(OCOMe) 以 水 、 丙酮 为溶剂， 生成 [Pd(2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N)(PPh3)][CF3SO3]
  参考文献：
  名称：

  Mononuclear and tetranuclear palladacycles with terdentate [C,N,N] and [C,N,O] Schiff base ligands. C–H versus C–Br activation reactions

  摘要：

  Reaction of the Schiff base ligands 2-Br-4,5-(OCH2O)C6H2C(H)=NCH2CH2NMe2 (a) and 4,5-(OCH2CH2)-C6H3C(H)=NCH2CH2NMe2 (b) with Pd(OAc)(2) or K-2[PdCl4] leads to the mononuclear cyclometallated compounds [Pd{2-Br-4,5-(OCH2O) C6HC(H)=NCH2CH2NMe2-C6,N,N}(OCOMe)] (1a) and [Pd{4,5-(OCH2-CH2) C6H2C(H)=NCH2CH2NMe2-C6,N,N}(Cl)] (1b), derived from C-H activation at the C6 carbon. Treatment of a with Pd-2(dba)(3) gave [Pd{4-5-(OCH2O) C6H2C(H)=NCH2CH2NMe2-C2,N,N}(Br)] (2a), via C-Br activation.The metathesis reaction of 1a with aqueous sodium chloride gave [Pd{2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N}(Cl)] (3a), with exchange of the acetate group by a chloride ligand. Treatment of the cyclometallated monomers 1a-3a with PPh3 in a 1:1 molar ratio yielded the mononuclear complexes [Pd{2-Br-4,5-(OCH2O) C6HC(H)=NCH2CH2NMe2-C6,N}(L)(PPh3)] (L: OAc, 4a; Cl, 5a) and [Pd{4-5-(OCH2O)C6H2C(H)=NCH2CH2NMe2-C2,N}(Br)(PPh3)] (6a), with Pd-NMe2 bond cleavage. However, treatment of a solution of 3a or 2a with silver trifluoromethanesulfonate, followed by reaction with PPh3 in acetone yielded the cyclometallated complexes [Pd{2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N}(PPh3)][CF3SO3] (7a) and [Pd{4-5-(OCH2O)C6H2C(H)=NCH2CH2NMe2-C2,N,N}(PPh3)][CF3SO3] (8a), respectively, where the Pd-NMe2 bond was retained.The reaction of the ligands 2-Br-4,5-(OCH2O)C6H2C(H)=N(2'-OH-5'-(BuC6H3)-Bu-t) (c) and 4,5-(OCH2CH2)-C6H3C(H)=N(2'-OH-5'-(BuC6H3)-Bu-t) (d) with Pd(OAc) 2 gave the tetranuclear complexes [Pd{2-Br-4, 5-(OCH2O)C6HC(H)=N(2'-O-5'-(BuC6H3)-Bu-t)-C6,N,O}](4) (1c) and [Pd{4,5-(OCH2CH2)C6H2C(H)=N(2'-O-5'-(BuC6H3)-Bu-t)-C6,N,O}](4) (1d), respectively. Treatment of 1c with PPh3 in 1:4 molar ratio, gave the mononuclear species [Pd{2-Br-4,5-(OCH2O)C6HC(H)=N(2'-(O)-5'-(BuC6H3)-Bu-t)-C6,N,O}(PPh3)] (2c) with opening of the polynuclear structure after P-O-bridging bond cleavage. The structure of compounds 2a, 1c and 1d has been determined by X-ray diffraction analysis. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.01.027
• 作为产物：
  描述：

  2-Br-4,5-(OCH2O)C6H2C(H)=NCH2CH2NMe2 、 palladium diacetate 以 甲苯 为溶剂， 以51%的产率得到Pd(2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N)(OCOMe)
  参考文献：
  名称：

  Mononuclear and tetranuclear palladacycles with terdentate [C,N,N] and [C,N,O] Schiff base ligands. C–H versus C–Br activation reactions

  摘要：

  Reaction of the Schiff base ligands 2-Br-4,5-(OCH2O)C6H2C(H)=NCH2CH2NMe2 (a) and 4,5-(OCH2CH2)-C6H3C(H)=NCH2CH2NMe2 (b) with Pd(OAc)(2) or K-2[PdCl4] leads to the mononuclear cyclometallated compounds [Pd{2-Br-4,5-(OCH2O) C6HC(H)=NCH2CH2NMe2-C6,N,N}(OCOMe)] (1a) and [Pd{4,5-(OCH2-CH2) C6H2C(H)=NCH2CH2NMe2-C6,N,N}(Cl)] (1b), derived from C-H activation at the C6 carbon. Treatment of a with Pd-2(dba)(3) gave [Pd{4-5-(OCH2O) C6H2C(H)=NCH2CH2NMe2-C2,N,N}(Br)] (2a), via C-Br activation.The metathesis reaction of 1a with aqueous sodium chloride gave [Pd{2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N}(Cl)] (3a), with exchange of the acetate group by a chloride ligand. Treatment of the cyclometallated monomers 1a-3a with PPh3 in a 1:1 molar ratio yielded the mononuclear complexes [Pd{2-Br-4,5-(OCH2O) C6HC(H)=NCH2CH2NMe2-C6,N}(L)(PPh3)] (L: OAc, 4a; Cl, 5a) and [Pd{4-5-(OCH2O)C6H2C(H)=NCH2CH2NMe2-C2,N}(Br)(PPh3)] (6a), with Pd-NMe2 bond cleavage. However, treatment of a solution of 3a or 2a with silver trifluoromethanesulfonate, followed by reaction with PPh3 in acetone yielded the cyclometallated complexes [Pd{2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N}(PPh3)][CF3SO3] (7a) and [Pd{4-5-(OCH2O)C6H2C(H)=NCH2CH2NMe2-C2,N,N}(PPh3)][CF3SO3] (8a), respectively, where the Pd-NMe2 bond was retained.The reaction of the ligands 2-Br-4,5-(OCH2O)C6H2C(H)=N(2'-OH-5'-(BuC6H3)-Bu-t) (c) and 4,5-(OCH2CH2)-C6H3C(H)=N(2'-OH-5'-(BuC6H3)-Bu-t) (d) with Pd(OAc) 2 gave the tetranuclear complexes [Pd{2-Br-4, 5-(OCH2O)C6HC(H)=N(2'-O-5'-(BuC6H3)-Bu-t)-C6,N,O}](4) (1c) and [Pd{4,5-(OCH2CH2)C6H2C(H)=N(2'-O-5'-(BuC6H3)-Bu-t)-C6,N,O}](4) (1d), respectively. Treatment of 1c with PPh3 in 1:4 molar ratio, gave the mononuclear species [Pd{2-Br-4,5-(OCH2O)C6HC(H)=N(2'-(O)-5'-(BuC6H3)-Bu-t)-C6,N,O}(PPh3)] (2c) with opening of the polynuclear structure after P-O-bridging bond cleavage. The structure of compounds 2a, 1c and 1d has been determined by X-ray diffraction analysis. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.01.027

文献信息

• Preparation of Imidazol‐2‐ylidene Carbene Palladacycles with Bi‐ and Tridentate Schiff Bases – Analyses of the Spectroscopic, Molecular Structure, and DFT Calculation Data
  作者：Leticia Naya、Digna Vázquez‐García、Alberto Fernández、Margarita López‐Torres、Vicente Ojea、Ismael Marcos、José M. Vila、Jesús J. Fernández

  DOI：10.1002/ejic.201501067

  日期：2016.1

  benzylideneimine palladacycles with potentially polydentate imidazol-2-ylidene silver carbene complexes produced new palladium organometallics with the N-heterocyclic carbene (NHC) coordinated to the palladium center. The NHCs bearing two carbene moieties show a bridging coordination mode across the two metal atoms and may also display a simultaneous bridging/chelating behavior. DFT calculations were performed

  用潜在的多齿咪唑-2-亚基银卡宾配合物处理适当的亚苄基亚胺钯环产生了新的钯有机金属化合物，其中 N-杂环卡宾 (NHC) 与钯中心配位。带有两个卡宾部分的 NHC 在两个金属原子之间显示出桥接配位模式，并且还可能同时显示出桥接/螯合行为。对化合物进行 DFT 计算，通过仔细检查 1H NMR 光谱观察到这些化合物的典型通量行为。13 的晶体和分子结构由 X 射线晶体学确定，并与 14 的计算数据进行对比，以确定后者的通量平衡的最有利配置。