fac-[Re(4,4'-dimethyl-2,2'-bipyridine)(CO)3(CH3CN)](PF6) | 395062-49-4

• 英文名称: fac-[Re(4,4'-dimethyl-2,2'-bipyridine)(CO)3(CH3CN)](PF6)
• 英文别名: fac-[Re(CO)3(5,5'-dimethyl-2,2'-bipyridine)(MeCN)](PF6)
• CAS: 395062-49-4
• 化学式: C₁₇H₁₅N₃O₃Re*F₆P
• 分子量: 640.496
• InChiKey: SSWVVRZZJLEBSW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  fac-[Re(4,4'-dimethyl-2,2'-bipyridine)(CO)3(CH3CN)](PF6) 在 三乙胺 作用下， 以 乙腈 为溶剂， 生成 [Re(4,4'-dimethyl-2,2'-bipyridine)(CO)3(CH3CN)]
  参考文献：
  名称：

  Involvement of a Binuclear Species with the Re−C(O)O−Re Moiety in CO₂ Reduction Catalyzed by Tricarbonyl Rhenium(I) Complexes with Diimine Ligands:  Strikingly Slow Formation of the Re−Re and Re−C(O)O−Re Species from Re(dmb)(CO)₃S (dmb = 4,4‘-Dimethyl-2,2‘-bipyridine, S = Solvent)

  摘要：

  Excited-state properties of fac-[Re(dmb)(CO)(3)(CH3CN)]PF6, [Re(dmb)(CO)(3)](2) (where dmb = 4,4'-dimethyl-2,2'-bipyridine), and other tricarbonyl rhenium(l) complexes were investigated by transient FTIR and UV-vis spectroscopy in CH3CN or THF. The one-electron reduced monomer, Re(dmb)(CO)(3)S (S = CH3CN or THF), can be prepared either by reductive quenching of the excited states of fac-[Re(dmb)(CO)(3)(CH3CN)]PF6 or by homolysis of [Re(dmb)(CO)(3)](2). In the reduced monomer's ground state, the odd electron resides on the dmb ligand rather than on the metal center. Re(dmb)(CO)(3)S dimerizes slowly in THF, k(d) = 40 +/- 5 M-1 s(-1). This rate constant is much smaller than those of other organometallic radicals which are typically 10(9) M-1 s(-1). The slower rate suggests that the equilibrium between the ligand-centered and metal-centered radicals is very unfavorable (K approximate to 10(-4)). The reaction of Re(dmb)(CO)(3)S with CO2 is slow and competes with the dimerization. Photolysis of [Re(dmb)(CO)(3)](2) in the presence of CO2 produces CO with a 25-50% yield based on [Re]. A CO2 bridged dimer, (CO)(3)(dmb)Re-CO(O)-Re(dmb)(CO)(3) is identified as an intermediate. Both [Re(dmb)(CO)(3)](2)(OCO2) and Re(dmb)(CO)(3)(OC(O)OH) are detected as oxidation products; however, the previously reported formato-rhenium species is not detected.

  DOI：

  10.1021/ja035960a

文献信息

• Synthesis, Photophysical Properties, and Photoinduced Luminescence Switching of Trinuclear Diimine Rhenium(I) Tricarbonyl Complexes Linked by an Isomerizable Stilbene-like Ligand
  作者：Shih-Sheng Sun、Alistair J. Lees

  DOI：10.1021/om0106027

  日期：2002.1.1

  trinuclear diimine rhenium(I) tricarbonyl complexes bridged by 1,3,5-tris(4-ethenylpyridyl)benzene (L1) or 1,3,5-tris(4-ethynylpyridyl)benzene (L2) have been synthesized and characterized. The L2-bridged complexes (group B) exhibit strong luminescence and long emission lifetimes in room-temperature solution which are typical of decay from 3MLCT excited states, while the L1-bridged complexes (group A)

  合成了由1,3,5-三（4-乙炔基吡啶基）苯（L1）或1,3,5-三（4-乙炔基吡啶基）苯（L2）桥接的两个系列的三核二亚胺rh（I）三羰基配合物，并表征。L2桥接的配合物（B组）在室温溶液中表现出强的发光性和长的发射寿命，这是从3种MLCT激发态衰减的典型现象，而L1桥接的配合物（A组）仅表现出非常弱的发光且寿命短。在相同的实验条件下，尽管发射位置和轮廓变化不大。A组络合物的低发射量子产率和短寿命归因于3的分子内敏化ππ*激发态位于桥接配体的烯烃键上，并伴随着随后的反式-顺式异构化过程。探索了不同的二亚胺配体取代基对三重态-三重态能量转移机制的影响。B组配合物的激发态衰变如下的LN之间观察到的线性关系的基础上，能隙法ķ NR和发射能量。