[Re(2,2'-bipyridine)(CO)₃(acetonitrile)]⁺ | 89708-63-4

• 英文名称: [Re(2,2'-bipyridine)(CO)₃(acetonitrile)]⁺
• 英文别名: [Re(bpy)(CO)₃(CH₃CN)]⁺；[Re(2,2'-bipyridyne)(CO)₃(acetonitrile)]⁺；{Re(bpy)(CO)3(MeCN)}(1+)；[Re(CO)3(2,2'-bipyridine)(CH3CN)](1+)；[Re(carbonyl)3(acetonitrile)(2,2'-bipyridine)](1+)；[Re(CO)3(bipy)(NCMe)](1+)；[Re(CO)3(bpy)(CH3CN)](1+)
• CAS: 89708-63-4
• 化学式: C₁₅H₁₁N₃O₃Re
• 分子量: 467.478
• InChiKey: CYIXTQMGFVJJLD-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：
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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：

  [Re(2,2'-bipyridine)(CO)₃(acetonitrile)]⁺ 、 di-tert-butyl 2,2′-((pyridin-4-ylmethyl)azanediyl)diacetate 在 NaHCO₃ 作用下， 以 乙腈 为溶剂， 以48%的产率得到[Re(carbonyl)3(NC5H4N(CH2CO2Bu-t)2)(2,2'-bipyridine)](OTf)
  参考文献：
  名称：

  First dinuclear Re/Tc complex as a potential bimodal Optical/SPECT molecular imaging agent

  摘要：

  在这项交流中，采用了一种新颖的合成路径来制备单分子中的双成像剂。双核Re(I)/Tc(I)复合物6，即[Re(CO)3(bipy){(4-PyrIDA)Tc(CO)3}]，是第一个基于Re/Tc的异金属组装体，可能作为潜在的双模态光学/SPECT探针。有趣的是，Re(I)复合物中间体4在生物应用中表现出显著的光物理特性。

  DOI：

  10.1039/c0dt01397h
• 作为产物：
  描述：

  [Re(bipyridine)(CO)4]Otf 在 tert-butylammonium hexafluorophosphate(V) 作用下， 以 乙腈 为溶剂， 生成 [Re(2,2'-bipyridine)(CO)₃(acetonitrile)]⁺
  参考文献：
  名称：

  一氧化碳释放通过电子转移催化的：的电化学和光谱研究[重（BPY-R）（CO）4 ]（OTF）络合物相关的CO 2还原†

  摘要：

  [Re（bpy- t Bu）（CO）4 ]（OTf）（bpy- t Bu =4,4'-二叔丁基-2,2'-联吡啶，OTf =三氟甲磺酸盐）（1）和[Re（bpy）（CO）4 ]（OTf）（py = 2,2'-联吡啶）（2）的合成和研究作为拟议的中间体通过Re（bpy-R）（CO）3 X电催化还原二氧化碳（CO 2）。这两种化合物在CO 2的循环伏安图中均显示出增强的电流响应。配合物1也通过X射线晶体学表征。1和2的红外光谱电化学（IR-SEC）表明，当阳离子四羰基化合物暴露于还原电势时，CO配体被标记，[Re（bpy-R）（CO）3（CH 3 CN）] +物种形成。建议通过一种电子转移催化的方法，其中催化量的还原物种传播配体交换反应。将催化量的插层石墨（KC 8）（一种化学还原剂）添加到1或2的溶液中，还可以定量形成[Re（bpy-R）（CO）3（CH 3 CN）] +，表示CO损失是由电子转移而不是电极本身催化的。

  DOI：

  10.1039/c3dt50612f

文献信息

• CO₂ capture by Mn(<scp>i</scp>) and Re(<scp>i</scp>) complexes with a deprotonated triethanolamine ligand
  作者：Hiroki Koizumi、Hiroyuki Chiba、Ayumi Sugihara、Munetaka Iwamura、Koichi Nozaki、Osamu Ishitani

  DOI：10.1039/c8sc04389b

  日期：——

  complexes could efficiently capture CO2 even from Ar gas containing only low concentration of CO2 such as 1% to be converted into fac-M(X2bpy)(CO)3(OC(O)OCH2CH2NR2) (M = Mn and Re). These CO2-capturing reactions proceeded reversibly and their equilibrium constants were >1000. The substituents of X2bpy strongly affected the CO2-capturing abilities of both Mn and Re complexes. The density functional theory

  通过催化剂捕获低浓度的CO 2可能对开发光催化和电催化CO 2还原系统有用。我们研究了两种配合物fac -Mn(X 2 bpy)(CO) 3 (OCH 2 CH 2 NR 2 ) 和fac -Re(X 2 bpy)(CO) 3 (OCH 2 CH 2 ) 的 CO 2捕获能力NR 2 ) (X 2 bpy = 4,4'-X 2 -2,2-联吡啶和R = –CH 2 CH 2OH)，它们可作为 CO 2还原的有效催化剂。即使从仅含有低浓度 CO 2 (如 1% ) 的 Ar 气中，两种配合物都可以有效捕获 CO 2以转化为fac -M(X 2 bpy)(CO) 3 (OC(O)OCH 2 CH 2 NR 2 ) （M = Mn 和 Re）。这些CO 2捕获反应可逆地进行并且它们的平衡常数>1000。X 2 bpy 的取代基强烈影响Mn 和Re 配合物的CO 2捕获能力。密度泛函理论 (DFT)
• Photoinduced linkage isomerization in new rhenium(I) tricarbonyl complexes coordinated to N-nitrite and O-nitrite
  作者：Sofía E. Domínguez、Pablo Alborés、Florencia Fagalde

  DOI：10.1016/j.poly.2013.10.002

  日期：2014.1

  The ambidentate nitrite ion, NO2-, is a biologically relevant species that can be coordinated to transition metals via the nitrogen or oxygen atom. Most of its physiological effects involve metalloproteins so it is important to understand the factors that control the predominance of one or another isomer. In this work, we present the syntheses and characterization by spectroscopy, electrochemistry and DFT calculations of new rhenium(l) tricarbonyl complexes with different polypyridyl ligands in the coordination sphere and with the nitrite ion coordinated through either its N- or O-atom. For two of them we have determined their crystal structures by X-ray diffraction and we have found that in the solid when the ancilliary ligand is bpy the N-binding mode is the most stable, while dmb is the ligand, the -CH3 substituents imposed the C-H (methyl group)center dot center dot center dot O-NO (nitrito) interactions favoring the O-binding mode. However, at room temperature in CH2Cl2 the nitro isomer is the most stable for both complexes in agreement with DFT calculations. Both complexes exhibit photoinduced linkage isomerism which could be of interesting in the design of new materials. Although nitro complexes are precursors of nitrosyl compounds, in this work the synthesis of the nitrosyl complexes as solid could not be possible because there is higher pi-backbonding from Re(l) to the carbonyl groups, or to the polypyridil ligands instead of to the NO group, which is pi-acceptor, in consequence the nitrosyl complexes are unstable and decompose immediately to the solvate complexes. (C) 2013 Elsevier Ltd. All rights reserved.
• On the Mechanism of Re(I)–Carboxylate Bond Cleavage by Perchloric Acid: A Kinetic and Spectroscopic Study
  作者：Ulises N. Fagioli、Fernando S. García Einschlag、Carlos J. Cobos、Gustavo T. Ruiz、Mario R. Féliz、Ezequiel Wolcan

  DOI：10.1021/jp206328q

  日期：2011.10.13

  We have studied the reaction between pz-CO2-Re(CO)(3)(bpy) and perchloric acid in acetonitrile by following the UV-vis and IR spectral changes in the reaction mixture. A fast equilibrium was found to be established between solvated protons, pz-CO2-Re(CO)3(bpy), and the protonated intermediate [pz-C(OH)O-Re(C0)(3)(bpy)](+) which finally yields pz-COOH and Re(CO)(3)(bpy)(CH3CN)(+) as reaction products. This intermediate has been characterized by UV-vis and IR spectroscopies and by DFT calculations. The fully optimized DFT/CPCM structures for pz-CO2-Re(CO)(3)(bpy) and [pz-C(OH)O-Re(CO)(3)(bpy)](+) were compared with the X-ray structure of pz-CO2-Re(CO)(3)(bpy). The structural parameters associated with the carboxyl group in the protonated intermediate are between those of pz-CO2-Re(CO)(3)(bpy) and pz-COOH. Multivariate curve resolution methods were employed to obtain the spectrum of the protonated intermediate and the concentration profiles from the full matrix of time resolved UV-vis spectra. The proposed mechanism was numerically simulated by using Runge-Kutta methods. Model parameters were estimated by nonlinear regression fitting of the concentration profiles, yielding values of log(K) = 4.9 +/- 03 and k = 0.16 +/- 0.03 min(-1) for the formation equilibrium constant and the decay rate constant of the protonated intermediate, respectively.