Mn(4,4′-di-tert-butyl-2,2′-bipyridine)(CO)₃Br | 1423120-49-3

• 英文名称: Mn(4,4′-di-tert-butyl-2,2′-bipyridine)(CO)₃Br
• 英文别名: fac-MnBr(4,4′-di-tert-butyl-2,2′-dipyridyl)(CO)3；Mn(CO)₃Br[4,4'-bis(tert-butyl)-2,2'-bipyridyl]；Mn(bpy-tBu)(CO)₃Br；fac-MnBr(tBu2-bpy)(CO)3
• CAS: 1423120-49-3
• 化学式: C₂₁H₂₄BrMnN₂O₃
• 分子量: 487.275
• InChiKey: QVNHNMFANVVNHJ-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

• 作为反应物：
  描述：

  Mn(4,4′-di-tert-butyl-2,2′-bipyridine)(CO)₃Br 以 乙腈 为溶剂， 生成 [Mn(bpy-tBu)(CO)₃]₂
  参考文献：
  名称：

  Manganese as a Substitute for Rhenium in CO₂ Reduction Catalysts: The Importance of Acids

  摘要：

  Electrocatalytic properties, X-ray crystallographic studies, and infrared spectroelectrochemistry (IRSEC) of Mn(bpy-tBu)(CO)(3)Br and [Mn(bpy-tBu)(CO)(3)(MeCN)](OTf) are reported. Addition of Bronsted acids to CO2-saturated solutions of these Mn complexes and subsequent reduction of the complexes lead to the stable and efficient production of CO from CO2. Unlike the analogous Re catalysts, these Mn catalysts require the addition of Bronsted acids for catalytic turnover. Current densities up to 30 mA/cm(2) were observed during bulk electrolysis using 5 mM Mn(bpytBu)(CO)(3)Br, 1 M 2,2,2-trifluoroethanol, and a glassy carbon working electrode. During bulk electrolysis at -2.2 V vs SCE, a TOF of 340 s(-1) was calculated for Mn(bpy-tBu)(CO)(3)Br with 1.4 M trifluoroethanol, corresponding to a Faradaic efficiency of 100 +/- 15% for the formation of CO from CO2, with no observable production of H-2. When compared to the analogous Re catalysts, the Mn catalysts operate at a lower overpotential and exhibit similar catalytic activities. X-ray crystallography of the reduced species, [Mn(bpy-tBu)(CO)(3)], shows a five. coordinate Mn center, similar to its rhenium analogue. Three distinct species were observed in the IR-SEC of Mn(bpy-tBu)(CO)(3)Br. These were of the parent Mn(bpy-tBu)(CO)(3)Br complex, the dimer [Mn(bpy-tBu)(CO)(3)](2), and the [Mn(bpy-tBu)(CO)(3)](2), and the [Mn(bpytBu)(CO)(3)](-) anion.

  DOI：

  10.1021/ic302391u
• 作为产物：
  描述：

  五羰基溴化锰(I) 、 4,4'-二叔丁基-2,2'-二吡啶 以 乙醚 为溶剂， 生成 Mn(4,4′-di-tert-butyl-2,2′-bipyridine)(CO)₃Br
  参考文献：
  名称：

  多壁碳纳米管上的取代 Mn(bpy)(CO)3X 型催化剂对 CO2 还原的空间效应揭示了关键的机理细节

  摘要：

  一系列具有系统取代基变化的 Mn(bpy-R)(CO) 3 Br (bpy-R = 4,4′-R-2,2′-联吡啶)配合物 (R = H, –Me, –Et, t Bu和-Ph)被固定在多壁碳纳米管(MWCNT)上并作为CO 2还原的电催化剂进行研究，以研究取代基对多相分子电催化的影响。对每个多相复合物的电化学响应和催化活性进行了表征，揭示了所研究的系列中的明显趋势。 Mn(bpy-Ph)(CO) 3 Br/MWCNT表现出最好的催化性能，在低过电势(η = 0.65 V)下产生CO，法拉第效率为72%，电流密度( J CO )为7.0 mA/cm 2）。向 bpy 配体添加空间体积可限制 Mn 0 –Mn 0二聚化，并导致在负电势较小时发生向双电子还原的转变。电活性催化剂的表观量与空间体积成反比，其中 Mn(bpy-Ph)(CO) 3 Br 在正常条件下的 CV 中没有表现出明显的法拉第

  DOI：

  10.1021/acscatal.3c05771
• 作为试剂：
  描述：

  二氧化碳 在 2,2,2-三氟乙醇 、 Mn(4,4′-di-tert-butyl-2,2′-bipyridine)(CO)₃Br 作用下， 以 乙腈 为溶剂， 生成 一氧化碳
  参考文献：
  名称：

  Manganese as a Substitute for Rhenium in CO₂ Reduction Catalysts: The Importance of Acids

  摘要：

  Electrocatalytic properties, X-ray crystallographic studies, and infrared spectroelectrochemistry (IRSEC) of Mn(bpy-tBu)(CO)(3)Br and [Mn(bpy-tBu)(CO)(3)(MeCN)](OTf) are reported. Addition of Bronsted acids to CO2-saturated solutions of these Mn complexes and subsequent reduction of the complexes lead to the stable and efficient production of CO from CO2. Unlike the analogous Re catalysts, these Mn catalysts require the addition of Bronsted acids for catalytic turnover. Current densities up to 30 mA/cm(2) were observed during bulk electrolysis using 5 mM Mn(bpytBu)(CO)(3)Br, 1 M 2,2,2-trifluoroethanol, and a glassy carbon working electrode. During bulk electrolysis at -2.2 V vs SCE, a TOF of 340 s(-1) was calculated for Mn(bpy-tBu)(CO)(3)Br with 1.4 M trifluoroethanol, corresponding to a Faradaic efficiency of 100 +/- 15% for the formation of CO from CO2, with no observable production of H-2. When compared to the analogous Re catalysts, the Mn catalysts operate at a lower overpotential and exhibit similar catalytic activities. X-ray crystallography of the reduced species, [Mn(bpy-tBu)(CO)(3)], shows a five. coordinate Mn center, similar to its rhenium analogue. Three distinct species were observed in the IR-SEC of Mn(bpy-tBu)(CO)(3)Br. These were of the parent Mn(bpy-tBu)(CO)(3)Br complex, the dimer [Mn(bpy-tBu)(CO)(3)](2), and the [Mn(bpy-tBu)(CO)(3)](2), and the [Mn(bpytBu)(CO)(3)](-) anion.

  DOI：

  10.1021/ic302391u

文献信息

• Mechanism of the Formation of a Mn-Based CO₂ Reduction Catalyst Revealed by Pulse Radiolysis with Time-Resolved Infrared Detection
  作者：David C. Grills、Jaime A. Farrington、Bobby H. Layne、Sergei V. Lymar、Barbara A. Mello、Jack M. Preses、James F. Wishart

  DOI：10.1021/ja501051s

  日期：2014.4.16

  Mn-formate precatalyst, which produces the bpy ligand-based radical. This radical undergoes extremely rapid (τ = 77 ns) formate dissociation accompanied by a free valence shift to yield the five-coordinate Mn-based radical, Mn(•)((t)Bu2-bpy)(CO)3. TRIR data also provide evidence that the Mn-centered radical does not bind acetonitrile prior to its dimerization. This reaction occurs with a characteristically

  使用将脉冲辐射分解与凝聚相中纳秒时间分辨红外 (TRIR) 光谱相结合的新技术，我们对锰基 CO2 还原电催化剂 [Mn((t )Bu2-bpy)(CO)3]2 ((t)Bu2-bpy = 4,4'-(t)Bu2-2,2'-联吡啶)，在乙腈中。TRIR 的使用首次允许直接观察该过程中涉及的所有中间体。将过量的 [(n)Bu4N][H ] 添加到 fac-MnBr((t)Bu2-bpy)(CO)3 的乙腈溶液中，导致其定量转化为 Mn-甲酸盐络合物 fac-Mn(OCHO) ((t)Bu2-bpy)(CO)3，它是用于电催化还原 的预催化剂。催化剂的形成是由甲酸锰预催化剂的单电子还原引发的，它产生基于 bpy 配体的自由基。该自由基经历极快的 (τ = 77 ns) 甲酸解离，伴随着自由价位移，产生五配位的 Mn 基自由基，Mn(•)((t)Bu2-bpy)(CO)3。TRIR 数据还提供了证据，证明以
• Ultrafast Spectroscopy of [Mn(CO)₃] Complexes: Tuning the Kinetics of Light-Driven CO Release and Solvent Binding
  作者：Wade C. Henke、Christopher J. Otolski、William N. G. Moore、Christopher G. Elles、James D. Blakemore

  DOI：10.1021/acs.inorgchem.9b02758

  日期：2020.2.17

  Manganese tricarbonyl complexes are promising catalysts for CO2 reduction, but complexes in this family are often photosensitive and decompose rapidly upon exposure to visible light. In this report, synthetic and photochemical studies probe the initial steps of light-driven speciation for Mn(CO)3(Rbpy)Br complexes bearing a range of 4,4'-disubstituted 2,2'-bipyridyl ligands (Rbpy, where R = tBu, H

  三羰基锰配合物是减少CO2的有前途的催化剂，但该族配合物通常是光敏性的，在暴露于可见光下会迅速分解。在这份报告中，合成和光化学研究探索了带有一系列4,4'-二取代的2,2'-联吡啶配体（Rbpy，其中R代表Mn（CO）3（Rbpy）Br配合物的光驱动物种形成的初始步骤= tBu，H，CF3，NO2）。乙腈中R = tBu，H和 的Mn（CO）3（Rbpy）Br配位化合物的瞬态吸收光谱测量显示，飞秒时间尺度上CO配体的超快损失，然后皮秒时间尺度上的溶剂配位。Mn（CO）3（ bpy）Br络合物在四种化合物中具有独特的优势，它们具有更长的激发态，不会经历CO释放或随后的溶剂配位。光敏复合物的光解动力学和溶剂配位动力学取决于双取代联吡啶配体的电子性质。结果表明，金属到配体的电荷转移（MLCT）和离解的配体场（dd）激发态均在超快光化学中起作用。综上所述，这些发现表明，可以通过适当设计的配