(CO)5ReRe(CO)3(bpy') | 130327-18-3

• 英文名称: (CO)5ReRe(CO)3(bpy')
• 英文别名: Re2(CO)8(4,4'-dimethyl-2,2'-bipyridine)
• CAS: 130327-18-3
• 化学式: C₂₀H₁₂N₂O₈Re₂
• 分子量: 780.738
• InChiKey: BZVHJGSNVGPYGN-UHFFFAOYSA-N

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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (CO)5ReRe(CO)3(bpy') 以 甲苯 为溶剂， 生成 {(CO)5Re}{Re(CO)3(bpy')}
  参考文献：
  名称：

  金属与金属键合的配合物的金属到配体的电荷转移光化学反应11.（CO）5MM'（CO）3（α-二亚胺）（M，M'Mn，Re）配合物的卤素原子和电子转移反应

  摘要：

  摘要本文描述了配合物（CO）5 MM'（CO）3（α-二亚胺）（M，M'Mm，Re）的三种类型的光反应。首先，讨论了在卤代烃存在下发生的卤素原子转移反应。与CCl 4和CBr 4的反应似乎是通过自由基链机理进行的。这种催化行为归因于由CX 4形成的CX 3自由基，该自由基可以引发次级卤素原子转移反应。因此，对于CH 2 Cl 2，确定了与卤代烃反应的量子产率，该CH 2 Cl 2由于其较高的C bondCl键解离能而未显示出催化行为。对于所有配合物，均获得了高量子产率（0.3-0.7），并且在整个配合物系列中这些值的变化归因于自旋轨道耦合的变化和非辐射衰变过程的速率。为了证实这些量子产率确实是专利化合物光解的量度，还在9，10-菲醌存在下研究了光反应。已知醌与CO损失和MM'键均质分解反应的主要光产物反应。从与CH 2 Cl 2和9,10-菲醌的反应的量子产率数据之间的一致性出发，得出的结论是（CO）5

  DOI：

  10.1016/s0020-1693(00)90385-2

文献信息

• Properties and dynamics of the σ(M′-Re)π∗ excited state of photoreactive dinuclear LnM′-Re(CO)3(α-diimine) (LnM′ = Ph3Sn, (CO)5Mn, (CO)5Re; α-diimine = bpy′, iPr-PyCa, iPr-DAB) complexes studied by time-resolved emission and absorption spectroscopies
  作者：Brenda D. Rossenaar、Elspeth Lindsay、Derk J. Stufkens、Antonín Vlček

  DOI：10.1016/s0020-1693(96)05203-6

  日期：1996.9

  The photophysics and photochemistry of the metal-metal bonded complexes L(n)M'Re(CO)(3)(alpha-diimine) (L(n)M'=Ph(3)Sn, (CO)(5)Re, (CO)(5)Mn; alpha-diimine = bpy', iPr-PyCa, iPr-DAB) have been studied. According to the time-resolved emission (80 K) and absorption (room temperature) spectra, the lowest excited state has a (3) sigma(M'-Re)pi* character. It is a bound state, which can only be populated by surface crossing from optically excited MLCT states. Homolysis of the metal-metal bond from the sigma pi* state is promoted by nucleophilic and chlorinated solvents. Exceptional in this respect is the complex Ph(3)SnRe(CO)(3)(bpy'), which is nearly photostable in non-chlorinated solvents. The lifetime of the (3) sigma pi* state decreases in the order alpha-diimine = bpy' > iPr-PyCa > iPr-DAB > pAn-DAB. This trend is mainly determined by the energy gap law. The L(n)M' dependence is more complicated because of an additional deactivating effect of an excited state distortion which depends on L(n)M'. At 80 K, the lifetime is determined by the weak coupling to the ground state; at room temperature by dissociation of M'-Re (with the exception of Sn-Re).