[Ir4(μ-2,6-pyridinedithiolato)2(1,5-cyclooctadiene)4] | 175397-55-4

• 英文名称: [Ir4(μ-2,6-pyridinedithiolato)2(1,5-cyclooctadiene)4]
• 英文别名: [Ir4(μ-2,6-pyridinedithiolate)2(1,5-cyclooctadiene)4]
• CAS: 175397-55-4
• 化学式: C₄₂H₅₄Ir₄N₂S₄
• 分子量: 1484.05
• InChiKey: BCGRYWULONTYPN-VEERNYDRSA-J

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

• 作为反应物：
  描述：

  thallium(I) hexafluorophosphate 、 [Ir4(μ-2,6-pyridinedithiolato)2(1,5-cyclooctadiene)4] 以 二氯甲烷 、 丙酮 为溶剂， 以90%的产率得到[TlIr4(μ-2,6-pyridinedithiolate)2(1,5-cyclooctadiene)4][PF6]
  参考文献：
  名称：

  Encapsulation of Thallium(I) by Tetranuclear Rhodium or Iridium Complexes:  Synthesis and Molecular Structure of Heterobimetallic Complexes Stabilized by s²−d⁸ Bonding Interactions

  摘要：

  Reactions of [M-4(mu-pyS(2))(2)(cod)(4)] (M = Rh, Ir; pyS(2) = 2,6-pyridinedithiolate, cod = 1,5-cyclooctadiene) with equimolar amounts of TlPF6 give the heterobimetallic complexes [TlM4(mu-pyS(2))(2)(cod)(4)] [PF6]. An outstanding change in the coordination modes of the bridging ligands occurs on the incorporation of the Tl atom into the tetranuclear complexes with the concomitant formation of two unprecedented TL-Rh bonds. The X-ray structure of the cation [TlRh4(mu-pyS(2))(2)(cod)(4)](+) (3(+)) shows an almost linear Rh-Tl-Rh bonded subunit with Tl-Rh separations of 2.7686(9) and 2.7706(9) Angstrom. An unusual sawhorse coordination environment of the thallium atom is completed by binding to two pyridine nitrogen atoms. Theoretical calculations on this Rh-Tl interaction also support the formation of Rh-Tl bonds, which is accompanied by a slight electron transfer from thallium to both "Rh(cod)" fragments. An additional partial oxidation of the thallium center agrees with the large shift low field of the resonance (observed at 2926 ppm) in the Tl-205{H-1} NMR spectrum of [TlRh4(mu-pyS(2))(2)(cod)(4)][PF6] (3) at 273 K. Moreover, complex 3 undergoes two irreversible one-electron anodic processes at 0.52 and 0.93 V (CH2Cl2, 0.1 V s(-1)). These waves are shifted to higher potential than those of the parent complex [Rh-4(mu-pyS(2))(2)(cod)(4)]. In addition, the cathodic response of this complex shows an irreversible reduction process at -1.48 V in which the Tl+ ion is extruded. Interestingly, upon excitation in the solid state at 77 K, complex 3 shows strong luminescence which can be related to the Rh-Tl-Rh chromophore.

  DOI：

  10.1021/ic980988m

文献信息

• Synthesis of Paramagnetic Tetranuclear Rhodium and Iridium Complexes with the 2,6-Pyridinedithiolate Ligand. Redox-Induced Degradation to Diamagnetic Triiridium Compounds
  作者：Miguel A. Casado、Jesús J. Pérez-Torrente、José A. López、Miguel A. Ciriano、Pablo J. Alonso、Fernando J. Lahoz、Luis A. Oro

  DOI：10.1021/ic001349q

  日期：2001.8.27

  methods, showed the three metal atoms within an angular arrangement. Both 2,6-pyridinedithiolate tridentate ligands bridge two metal-metal bonded d(7) centers in pseudo octahedral environments and one d(8) square-planar iridium center. An interpretation of the EPR spectra of the 63-electron mixed-valence paramagnetic tetranuclear complexes suggests that the unpaired electron is delocalized over two

  四核配合物[M4（mu-PyS2）2（二烯烃）4] [PyS2 = 2,6-吡啶二硫代磺酸盐; M ＝ Rh，二烯烃＝ cod（1，5-环辛二烯）（1），tfbb（四氟苯并[5，6]双环[2.2.2] octa-2，5，7-三烯）（2）；M = Ir，二烯烃=鳕鱼（3），tfbb（4）]在二氯甲烷中的铂圆盘电极上以化学试剂可及的电势显示出两个单电子氧化。铑四核配合物被轻度单电子氧化剂如[Cp2Fe]（）选择性氧化为单阳离子配合物[Rh4（mu-PyS2）2（二烯烃）4]（+）（1（+），2（+）） +）或[N（C6H4Br-4）3]（+），并分离为PF6（-），BF4（-）和ClO4（-）盐。银盐对于与铑配合物1和2的反应起无害的单电子氧化剂的作用，因为它们会产生微溶的配位聚合物。通过使3与1摩尔当量的Ag 反应，以四氟硼酸盐的形式得到配合物[Ir4（mu-PyS2）2（cod）4]（