fac-[Re(CO)3(NN'-diisopropylethane-1,2-diimine)Cl] | 64521-74-0

• 英文名称: fac-[Re(CO)3(NN'-diisopropylethane-1,2-diimine)Cl]
• 英文别名: ReCl(CO)3(N,N'-diisopropyl-1,4-diaza-1,3-butadiene)；Re(Cl)(CO)3(N,N'-diisopropyl-1,4-diaza-1,3-butadiene)；[ReCl(CO)3(di-iPr-N,N-1,4-diazabutadiene)]；Re(Cl)(CO)3(i-Pr-DAB)
• CAS: 64521-74-0
• 化学式: C₁₁H₁₆ClN₂O₃Re
• 分子量: 445.92
• InChiKey: PCKGPQUFTFWHLX-YYSZEHGHSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 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：

  fac-[Re(CO)3(NN'-diisopropylethane-1,2-diimine)Cl] 、 silver trifluoromethanesulfonate 以 四氢呋喃 为溶剂， 生成 [Re(CF3SO3)(CO)3(di-iPr-N,N-1,4-diazabutadiene)]
  参考文献：
  名称：

  [Re（NCS）（CO）3（α-diimine）]的配体至二亚胺/金属至二亚胺的电荷转移激发态（α-二亚胺= 2,2'-联吡啶，di-iPr-N， N-1，4-二氮杂丁二烯）。光谱和计算研究。

  摘要：

  两个新的复合物fac- [Re（NCS）（CO）3（N，N）]（N，N = 2,2'-联吡啶（bpy），di-iPr-N，N-1,4-二氮杂丁二烯（iPr -DAB））的合成，并通过X射线衍射确定其分子结构。实验测量了紫外可见吸收，共振拉曼光谱，发射光谱和皮秒时间分辨的红外光谱，并使用TD-DFT进行了计算。仅在将溶剂（MeCN）包括在计算中并且在TD-DFT级别上完全优化了激发态结构的情况下，才能在实验光谱与计算的基态光谱和激发态光谱之间取得良好的一致性。通过比较计算和实验的红外光谱，TD-DFT将bpy和iPr-DAB配合物的最低激发态指定为3aA'。激发态寿命为23 ns左右。对bpy和DAB复合物分别测定了625 ps，在室温下的液体溶液中。在77 K玻璃中观察到的[Re（NCS）（CO）3（bpy）]的双指数发射衰减（1.3、2.7微米）表明存在两个未平衡的发射态。两种配合物的低电子跃迁和激发态都具有混合的NCS->

  DOI：

  10.1021/jp044114z
• 作为产物：
  描述：

  四氯化碳 、 Re(SnPh3)(CO)3(N,N'-diisopropyl-1,4-diaza-1,3-butadiene) 、 二氯甲烷 以 二氯甲烷 为溶剂， 生成 fac-[Re(CO)3(NN'-diisopropylethane-1,2-diimine)Cl] 、 三苯基氯化锡
  参考文献：
  名称：

  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

  摘要：

  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).

  DOI：

  10.1016/s0020-1693(96)05203-6