(2,2'-bipyridine)chloridotricarbonylrhenium(I) anion radial | 128496-76-4

• 英文名称: (2,2'-bipyridine)chloridotricarbonylrhenium(I) anion radial
• 英文别名: (η2-2,2'-bipyridine)chlorotricarbonylrhenium(I)(1-)；[(2,2'-bipyridine)Re(CO)3Cl](.-)；(2,2'-bipyridine)Re(CO)3Cl(1-)；Re(CO)3(2,2'-bipyridine)Cl(-)；Re(CO)₃(2,2’-bipyridine)Cl^-；[Re(I)(bpy•-)(CO)₃Cl]^-
• CAS: 128496-76-4
• 化学式: C₁₃H₈ClN₂O₃Re
• 分子量: 461.878
• InChiKey: NYVLTCWCOYBQQI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  tricarbonyl(2,2'-bipyridine)chlororhenium(I) 以 丙酮 为溶剂， 生成 (2,2'-bipyridine)chloridotricarbonylrhenium(I) anion radial
  参考文献：
  名称：

  具有[Ru（bpy）2 ] 2+和re（CO）3（卤化物）片段的α-二亚胺配合物的相关电子结构的证据

  摘要：

  Re（CO）3 X，XCl，Br的低空空位轨道由单核和二核配合物的EPR光谱分析得出，其中单个还原的α-二亚胺配体2,2'-联吡啶和偶氮-2,2su'-联吡啶。尽管光谱分辨率较差，但仍可确定185,187 Re的强度和未解析的卤化物超细分裂。讨论了Re（CO）3 X和[Ru（bpy）2 ] 2+片段的α-二亚胺配合物的光谱相似性，涉及它们的相关电子结构和光催化反应性。

  DOI：

  10.1016/0009-2614(87)80574-2

文献信息

• A Thiourea Tether in the Second Coordination Sphere as a Binding Site for CO₂ and a Proton Donor Promotes the Electrochemical Reduction of CO₂ to CO Catalyzed by a Rhenium Bipyridine-Type Complex
  作者：Eynat Haviv、Dima Azaiza-Dabbah、Raanan Carmieli、Liat Avram、Jan M. L. Martin、Ronny Neumann

  DOI：10.1021/jacs.8b05658

  日期：2018.10.3

  moiety in the second coordination sphere. Using the well-known fac-Re(I)bipyridine(CO)3Cl complex as a starting point, the bipyridine ligand was modified in the second coordination sphere with a thiourea tether that is known to form hydrogen bonds with carbonyl moieties. The resulting Re(I) catalyst was an excellent electrocatalyst for the selective reduction of CO2 to CO, with a turnover frequency of

  近年来，CO2 的电化学还原得到了广泛的研究，希望通过详细的机理理解可以实现找到具有高周转频率和低还原电位的稳定催化剂的目标。在二氧化碳氢化酶的催化循环中，已表明还原的金属中心与 反应形成羧酸盐中间体，该中间体通过使用第二配位球中的组氨酸部分的氢键稳定。使用众所周知的 fac-Re(I) 联吡啶 (CO)3Cl 复合物作为起点，联吡啶配体在第二个配位球中用硫脲系链进行修饰，硫脲系链已知可与羰基部分形成氢键。所得的 Re(I) 催化剂是一种极好的将 选择性还原为 CO 的电催化剂，其转换频率为 3040 s-1。 与硫脲系链的结合可通过 1H NMR 观察到，NOE 实验表明硫脲基团的氢原子是不稳定的。进一步的实验表明，硫脲部分也是一个局部质子源，添加外部质子源实际上会抑制催化作用。通过 DFT 计算解释了动力学同位素效应的缺失，该计算表明质子总是跳到最近的 氧
• Origin of electronic absorption spectra of MLCT-excited and one-electron reduced 2,2′-bipyridine and 1,10-phenanthroline complexes
  作者：Stanislav Záliš、Cristina Consani、Amal El Nahhas、Andrea Cannizzo、Majed Chergui、František Hartl、Antonín Vlček

  DOI：10.1016/j.ica.2011.02.084

  日期：2011.8

  UV-Vis absorption spectra of one-electron reduction products and (MLCT)-M-3 excited states of [(ReCl)-Cl-I(CO)(3)-(N, N)] (N, N = 2,2'-bipyridine, bpy; 1,10-phenanthroline, phen) have been measured by low-temperature spectroelectrochemistry and UV-Vis transient absorption spectroscopy, respectively, and assigned by open-shell TD-DFT calculations. The characters of the electronic transitions are visualized and analyzed using electron density redistribution maps. It follows that reduced and excited states can be approximately formulated as [(ReCl)-Cl-I(CO)(3)(N,N-center dot)] and /[(ReCl)-Cl-II(CO)(3)(N,N-center dot)], respectively. UV-Vis spectra of the reduced complexes are dominated by IL transitions, plus weaker MLCT contributions. Excited-state spectra show an intense band in the UV region of similar to 50% IL origin mixed with LMCT (bpy, 373 nm) or MLCT (phen, 307 nm) excitations. Because of the significant IL contribution, this spectral feature is akin to the principal IL band of the anions. In contrast, the excited-state visible spectral pattern arises from predominantly LMCT transitions, any resemblance with the reduced-state visible spectra being coincidental. The Re complexes studied herein are representatives of a broad class of metal alpha-diimines, for which similar spectroscopic behavior can be expected. (C) 2011 Elsevier B. V. All rights reserved.
• 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)
  作者：Yukiko Hayashi、Shouichi Kita、Bruce S. Brunschwig、Etsuko Fujita

  DOI：10.1021/ja035960a

  日期：2003.10.1

  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.