Pd(acetylthiophene 4-methylthiosemicarbazone)(PPh3) | 1333226-16-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Pd(acetylthiophene 4-methylthiosemicarbazone)(PPh3)
• 英文别名: Pd(κ3-C4,N3,S-2-acetylthiophene-N-methylthiosemicarbazonato)
• CAS: 1333226-16-6
• 化学式: C₂₆H₂₄N₃PPdS₂
• 分子量: 580.022
• InChiKey: GPNPCJFKADLADU-SGLXJCBISA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  三苯基膦 在 N(C₂H₅)3 作用下， 以 甲苯 、 乙腈 为溶剂， 生成 Pd(acetylthiophene 4-methylthiosemicarbazone)(PPh3)
  参考文献：
  名称：

  Thiosemicarbazonates of palladium(II): The presence of methyl/phenyl substituents (R2) at C2 carbon atom induces C–H activation of R1 rings of thiosemicarbazones {R1R2C2N3–N2H–C1(S)–N1HR3}

  摘要：

  A series of palladium(II) complexes involving C-H and N-H bond activations of the R-1 rings of thiosemicarbazones {R-1(R-2)C-2-N-3-N-2(H)-C-1(=S)-(NHR3)-H-1; R-1, R-2: thiopheneyl, Me, H2L1 (R-3 = Me), H2L2 (R-3 = Ph); R-1, R-2: Ph, Me, H2L3 (R-3 = Me), H2L4 (R-3 = Ph); R-1, R-2: Ph, Ph, H2L5 (R-3 = Me), H2L6 (R-3 = Ph) and R-1, R-2: pyrrole, Me, H2L7 (R-3 = Me), H2L8 (R-3 = Ph)} are described. Methyl group (R-2) at C-2 carbon in H2L1 and H2L2 induced C-H bond activation of the thiopheneyl ring and formed cyclometallated complexes, [Pd(kappa(3)-C-4,N-3,S-L)(PPh3)] (L - L-1, 1; L-2, 2). Similarly, phenyl rings (R-1) in H2L3, H2L4, H2L5, H2L6 at C-2 carbon have shown C-H activations forming cyclometallated complexes, [Pd(kappa(3)-C-4,N-3, S-L)(PPh3)] (L = L-3, 3; L-4, 4; L-5, 5; L-6, 6). However, pyrrole ring did not exhibit similar C-H activation behavior, rather involved N-H activation and formed complexes, [Pd(kappa(3)-N-4,N-3, S-L)(PPh3)] {L = L-7, 7; L-8, 8}. All these complexes have been characterized with the help of analytical data, spectroscopic techniques (IR, H-1 and P-31 NMR), and single crystal X-ray crystallography (1, 2, 4, 5, 7 and 8). The thiosemicarbazone ligands behave as dinegative C-4, N-3, S-chelating in 1-6 and N-4, N-3, S-chelating in complexes 7 and 8. Interestingly, complexes 2, 4 and 8, with phenyl substituent at N-1 atom, have two independent molecules in their respective crystal lattices. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.11.028

文献信息

• Cyclopalladation of thiophene-substituted thiosemicarbazones
  作者：Henning Weiss、Fabian Mohr

  DOI：10.1016/j.jorganchem.2011.06.021

  日期：2011.10

  The thiosemicarbazones obtained from the condensation of thiosemicarbazide or 4,4′-dimethylthiosemicarbazide with 2-acetylthiophene react with K2PdCl4 in the presence of a base to give dark, poorly soluble materials in high yields. Treatment of these oligomeric compounds with Ph3P, dppe or dppf gives monomeric palladium(II) phosphine complexes in which the deprotonated thiosemicarbazones coordinate

  在碱的存在下，由硫代氨基脲或4,4'-二甲基硫代氨基脲与2-乙酰基噻吩的缩合反应获得的硫代氨基脲与K 2 PdCl 4反应，以高收率得到深色的难溶物质。用Ph 3 P，dppe或dppf处理这些低聚化合物可得到单体钯（II）膦配合物，其中去质子化的硫代半氨基甲酮通过C3环金属化的噻吩环，亚胺氮原子和硫原子以三齿形与金属配位。通过几种衍生物的X射线结构分析证实了这种配位模式。