[Re(4,4'-dicarboxy-2,2'-bipyridine)(CO)3Cl] | 116840-69-8

• 英文名称: [Re(4,4'-dicarboxy-2,2'-bipyridine)(CO)3Cl]
• 英文别名: [Re(CO)₃(Cl)(2,2’-bipyridyl-4,4’-dicarboxylic acid)]；[Re(CO)₃(Cl)(dcbH₂)]；[Re(4,4′-dicarboxylic acid-2,2′-bipyridine)Cl(CO)₃]；Re(CO)3(Cl)(2,2'-bipyridine-4,4'-carboxylate)；[Re(4,4'-dicarboxyl-2,2'-bipyridine)(CO)3Cl]；Re(CO)3Cl(4,4'-dicarboxy-2,2'-bipyridine)；[Re(4,4'-(CO2H)2-bpy)(CO)3Cl]
• CAS: 116840-69-8
• 化学式: C₁₅H₈ClN₂O₇Re
• 分子量: 549.898
• InChiKey: YFRQDJFKOFCIMT-UHFFFAOYSA-M

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：
  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：

  [Re(4,4'-dicarboxy-2,2'-bipyridine)(CO)3Cl] 以 四氢呋喃 为溶剂， 生成 [Re(4,4'-dicarboxyl-2,2'-bipyridine)(CO)3(4-pyridinecarboxaldehyde azine)](CF3SO3)*2H2O*(acetone)
  参考文献：
  名称：

  Improvement of the Dynamic Range of pH Sensing by Using a Luminescent Tricarbonylpolypyridylrhenium(I) Complex with Three Different Protonation Sites

  摘要：

  The complex [Re(4,4'-(CO2H)(2)-bpy)(CO)(3)(4,4'-bpy)](CF3SO3), 1 (4,4'-(CO2H)(2)-bpy = 4,4'-dicarboxyl-2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine), synthesized and characterized by spectroscopic techniques, displays a strong dependence of its photophysical properties on pH. From both emission intensity and lifetime measurements at different pH values, three values for the protonation constants of the excited states have been determined (pK(a1)* = 1.8 +/- 0.1, pK(a2)* = 3.9 +/- 0.1, and pK(a3)* = 5.6 +/- 0.1). The unusual bell-shaped variations of these photophysical properties can be accounted for by the changes of energy level orderings induced by each protonation, as confirmed by time-dependent density functional theory (TD-DFT) calculations. Since the solubility, stability, and dynamic range of pH sensing by 1 have been improved with respect to similar tricarbonylpolypyridylrhenium(I) complexes, we conclude that 1 can be used as an efficient molecular switch of the on-off-on type.

  DOI：

  10.1021/ic802203d
• 作为产物：
  描述：

  五羰基氯铼(I) 、 2,2'-联吡啶-4,4'-二甲酸 以 甲醇 、 甲苯 为溶剂， 生成 [Re(4,4'-dicarboxy-2,2'-bipyridine)(CO)3Cl]
  参考文献：
  名称：

  Re（bipy-tBu）（CO）3 Cl改善了二氧化碳还原的催化活性：红外光谱电化学和机理研究

  摘要：

  制备并研究了5种Re（bipy）（CO）3 Cl络合物，其中bipy为4,4'-二羧基-2,2'-联吡啶（1），2,2'-联吡啶（2），4,4'-二甲基-2,2'-联吡啶（3），4,4'-二叔丁基-2,2'-联吡啶（4）和4,4'-二甲氧基-2,2'-联吡啶（5） 。从这一组中，发现了一种显着改进的催化剂Re（bipy-tBu）（CO）3 Cl（4），用于将二氧化碳还原为一氧化碳。该络合物在氩气下显示出两种单电子还原，一种在-1445 mV（vs SCE）时可逆，而另一种在-1830 mV时不可逆。在CO 2下第二个不可逆波在电流中显示出很大的催化增强作用。使用Levich-Koutecky方法确定扩散系数（中性络合物为1.1×10 -5 cm 2 / s，单个还原物为8.1×10 -6 cm 2 / s），电化学系数为二阶常数测量了1000 M -1 s -1的CO 2还原量。进行本体电

  DOI：

  10.1021/ic1008363
• 作为试剂：
  描述：

  二氧化碳 在 三乙醇胺 、 [Re(4,4'-dicarboxy-2,2'-bipyridine)(CO)3Cl] 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 一氧化碳
  参考文献：
  名称：

  Effect of ligand derivatization at different positions on photochemical properties of hybrid Re(I) photocatalysts

  摘要：

  Hybrid CO2-reduction photocatalysts based on Re(bpy)(CO)(3)Cl, where bpy is 2,2'-bipyridine, were synthesized in order to investigate the effect of different ligand derivatization strategies on photochemical properties of the hybrid Re(I) systems. Derivatization of the bpy ligand was carried out at the 4,4'- and 5,5'-positions with electron-withdrawing amide groups. The derivatized ligands were grafted on mesoporous silica via a dipodal silane coupling agent and were further coordinated with Re(I). The synthesized hybrid photocatalysts were studied using spectroscopic techniques, including UV-visible, in situ infrared and electron paramagnetic resonance (EPR) spectroscopy, and tested in photochemical CO2 reduction. An interesting light-induced color change was observed for the hybrid photocatalyst involving derivatization of the bpy ligand at the 5,5'-positions. Combined UV-visible and EPR studies indicated that in the reduced form of this hybrid photocatalyst electron density was more localized on the bpy ligand than on the Re(I) center. Further studies with in situ infrared spectroscopy demonstrated possible formation of a carbonate-bridged binuclear Re(I) species on this hybrid photocatalyst. Our results are particularly relevant to developing new molecular and hybrid photocatalytic systems which involve extensive derivatization of coordinating ligands with functional groups for improved solar energy conversion. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2015.10.034

文献信息

• Re ^I Tricarbonyl Complexes as Coordinate Covalent Inhibitors for the SARS‐CoV‐2 Main Cysteine Protease
  作者：Johannes Karges、Mark Kalaj、Milan Gembicky、Seth M. Cohen

  DOI：10.1002/anie.202016768

  日期：2021.5.3

  syndrome—coronavirus 2 (SARS‐CoV‐2) has impacted the quality of life and cost hundreds‐of‐thousands of lives worldwide. Based on its global spread and mortality, there is an urgent need for novel treatments which can combat this disease. To date, the 3‐chymotrypsin‐like protease (3CLpro), which is also known as the main protease, is considered among the most important pharmacological targets. The vast majority

  自爆发以来，严重急性呼吸系统综合症冠状病毒 2 (SARS-CoV-2) 影响了生活质量，并导致全世界数十万人丧生。鉴于其在全球的传播和死亡率，迫切需要能够对抗这种疾病的新疗法。迄今为止，3-胰凝乳蛋白酶样蛋白酶（3CL pro ）也被称为主要蛋白酶，被认为是最重要的药理学靶点之一。绝大多数研究的 3CL前体抑制剂都是有机非共价结合剂。在此，建议使用无机配位共价结合剂来减弱蛋白酶的活性。 Re 三羰基复合物被鉴定为 3CL pro的协调共价酶抑制。初步研究表明 3CL pro对几种人类蛋白酶具有选择性抑制作用。这项研究首次展示了金属配合物作为 3CL半胱氨酸蛋白酶抑制剂的例子。
• Synthesis and characterization of rhenium(I) 4,4′-dicarboxy-2,2′-bipyridine tricarbonyl complexes for solar energy conversion
  作者：Venugopal Komreddy、Kevin Ensz、Huy Nguyen、D. Paul Rillema

  DOI：10.1016/j.ica.2020.119815

  日期：2020.10

  Abstract The synthesis of a series of rhenium(I) tricarbonyl complexes containing 4,4′-dicarboxy-2,2′-bipyridine (dcbpy) and various halide or pseudohalide ligands is reported. Deprotonation of the carboxylates occurs in basic medium resulting in upfield 1H NMR shifts for the protons of the carboxyl groups attached to 2,2′-bipyridine. Metal-to-ligand charge transfer (MLCT) due to dπ → π* transitions

  摘要报道了一系列含4,4'-二羧基-2,2'-联吡啶（dcbpy）和各种卤化物或拟卤化物配体的tri（I）三羰基配合物的合成。羧酸盐的去质子化在碱性介质中发生，导致连接到2,2'-联吡啶的羧基质子的高场1H NMR位移。由于dπ→π*跃迁导致的金属到配体的电荷转移（MLCT）在卤化物序列中从Re（dcbpy）（CO）3F的382 nm系统地转移到Re（dcbpy）（CO）3I的436 nm。这些化合物在600–650 nm范围内发射，并且发射寿命大于50 ns。在Gratzel电池中使用TiO2-Re（dcbpy）（CO）3X（X = F，CN，SCN，Br，I）和光阳极时，太阳能转换效率不到1％。
• Effect of Li ions doping into p-type semiconductor NiO as a hole injection/transfer medium in the CO2 reduction sensitized/catalyzed by Zn-porphyrin/Re-complex upon visible light irradiation
  作者：Ryosuke Nakazato、Yoki Kou、Daisuke Yamamoto、Tetsuya Shimada、Tamao Ishida、Shinsuke Takagi、Hirokazu Munakata、Kiyoshi Kanamura、Hiroshi Tachibana、Haruo Inoue

  DOI：10.1007/s11164-020-04334-1

  日期：2021.1

  Re(dicarboxybipyridine)(CO)3(CH3CN) as the catalyst co-adsorbed on p-type semiconductor, NiO, were adopted for the MCSS catalyzed photoreduction of CO2 into CO. NiO was prepared by sol/gel method, and Li ions were doped to promote the hole carrier mobility with the amount of [Li]/[Ni] = 0, 3, 6, 9%, respectively. The conductivity of NiO increased linearly with the doping amount of Li ions, while the photoreduction

  由增敏剂和共吸附在半导体上的分子催化剂组成的分子催化剂敏化系统（MCSS）应该是人​​造光合作用系统的有希望的候选者之一，该系统可以用水将CO 2固定为电子供体。在此，采用共聚吸附在p型半导体NiO上的单羧基苯基三甲硅烷基卟啉锌（II）和Re（二羧基联吡啶）（CO）3（CH 3 CN）作为催化剂用于MCSS催化的CO 2光还原。通过溶胶/凝胶法制备NiO，并掺杂Li离子以提高空穴载流子迁移率，分别为[Li] / [Ni] = 0、3、6、9％。NiO的电导率随Li离子的掺杂量线性增加，而MCSS中CO 2的光还原作用在Li离子的3％，6％的掺杂下有所增强，而在9％的较高掺杂量下则有所减弱。明显矛盾的增强和延迟都通过锂离子掺杂对NiO内空穴载流子迁移率的促进作用得以成功解释，该促进作用既增强了与自由基离子对的电荷分离，又增强了NiO中自由空穴载流子的电荷复合。
• Heteromultimetallic compounds based on polyfunctional carboxylate linkers
  作者：Khairil A. Jantan、James M. McArdle、Lorenzo Mognon、Valentina Fiorini、Luke A. Wilkinson、Andrew J. P. White、Stefano Stagni、Nicholas J. Long、James D. E. T. Wilton-Ely

  DOI：10.1039/c8nj06455e

  日期：——

  trimetallic compounds are accessible using polyfunctional linkers with carboxylic acid and alkynyl or pyridyl donor combinations. This versatile approach affords reaction at a specific donor site in each case, to accommodate both ruthenium(II) or osmium(II) units and also rhenium and gold centres. Due to the orientation of the nitrogen donors of the bipyridyl moiety in 2,2′-bipyridine-4,4′-dicarboxylic acid

  使用具有羧酸和炔基或吡啶基供体组合的多官能连接基可得到一系列的同核和杂核，双金属和三金属化合物。这种通用的方法可在每种情况下在特定的供体位点提供反应，以容纳钌（II）或（（II））单位以及rh和金中心。由于2,2'-联吡啶-4,4'-二羧酸中联吡啶部分的氮供体的取向，出于空间考虑，必须以一定顺序进行金属添加。晶体学研究了一个实例，以增加对所有配合物进行的光谱和分析表征。光物理研究揭示了结合第二排或第三排过渡金属中心的效果。通过使用同时具有羧酸和炔基官能度的连接基，即1,1'-乙炔基二茂铁羧酸，该方法得到了扩展。这样可以使羧酸酯供体进行初始配位，然后形成与另一种金属的乙炔基或乙烯基桥，3 Ru 2 Au 2的例子。对后一种化合物进行了初步的电化学研究。
• Photophysical Properties of Chlorophyll Derivatives Linked with Rhenium Bipyridine Complexes
  作者：Yuichi Kitagawa、Shin Ogasawara、Daisuke Kosumi、Hideki Hashimoto、Hitoshi Tamiaki

  DOI：10.1246/bcsj.20140326

  日期：2015.2.15

  Since photochemical CO2 reduction using long wavelength regions of sunlight is important, we have reported the first photochemical CO2 reduction with red visible light (>650 nm) by using a synthetic chlorophyll derivative covalently linked with a rhenium bipyridine complex. In the reported system, electron/energy transfer from the photoexcited chlorophyll to the catalytic Re complex was not so effective. To accelerate the process for achieving efficient photochemical reduction of CO2, we controlled the redox potential of Re complex and improved the chlorophyll donor by a simple modification. As a result, we achieved strong quenching of the excited states of a 131-deoxochlorophyll derivative with a rhenium bipyridine complex in a molecule.

  由于使用太阳光长波长区域的光化学二氧化碳还原非常重要，因此我们报道了通过使用与铼联吡啶络合物共价连接的合成叶绿素衍生物，利用红色可见光（> 650 nm）进行光化学二氧化碳还原。在报道的系统中，从光激发叶绿素到催化铼络合物的电子/能量转移并不那么有效。为了加速实现高效光化学还原CO2的过程，我们通过简单的修饰控制了Re络合物的氧化还原电位并改善了叶绿素供体。结果，我们实现了分子中具有联吡啶铼络合物的 131-脱氧叶绿素衍生物的激发态的强猝灭。