fac-[Mn(4,4′-dimethyl-2,2′-bipyridine)(CO)₃Br] | 210919-96-3

• 英文名称: fac-[Mn(4,4′-dimethyl-2,2′-bipyridine)(CO)₃Br]
• CAS: 210919-96-3
• 化学式: C₁₅H₁₂BrMnN₂O₃
• 分子量: 403.114
• InChiKey: CMWWBZZDSSWSSO-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：

  fac-[Mn(4,4′-dimethyl-2,2′-bipyridine)(CO)₃Br] 以 乙腈 为溶剂， 生成 一氧化碳
  参考文献：
  名称：

  Impact of Mn(I) photoCORM ligand set on photochemical intermediate formation during visible light-activated CO release

  摘要：

  Tricarbonylmanganese(I) complexes are known to be robust photo-activated CO releasing molecules, or photoCORMs, yet their photochemical ligand exchange mechanisms as a function of ligand set are not well understood. The work reported herein presents a series of fac-[Mn(NN)(CO)(3)(L)](n+) compounds, in which NN= 4,4'-dimethylester-2,2'-bipyridine (dmebpy), 2,2'-bipyridine (bpy), or 4,4'-dimethyl-2,2'-bipyridine (Me(2)bpy), and L= Br- (n= 0) or py (n= 1), which were designed to probe the impact of both NN and L on the photochemical ligand exchange mechanism and efficiency in coordinating solvent. Replacing the pi-donor Br- with pi-acceptor py not only stabilizes the Mn(I)-based HOMO, blue shifting the absorption maximum and decreasing the quantum yield for CO dissociation (Phi(CO)), but also influences the structures of the observed photochemical intermediates. This study reveals, through FTIR and H-1 NMR studies, that the first CO loss occurs cis to L when L = Br-, while the first CO loss occurs trans to L when L = py. Varying the pi-acidity of NN provides the expected increase in Phi(CO) as NN pi-acidity increases (Me(2)bpy < bpy < dmebpy), although the identity of L appears to play a larger role in both the ligand exchange efficiency and the formation of photochemical intermediates.

  DOI：

  10.1016/j.ica.2019.119206
• 作为产物：
  描述：

  4,4'-二甲基-2,2'-联吡啶 、 五羰基溴化锰(I) 以 乙醚 为溶剂， 反应 3.0h， 以96%的产率得到fac-[Mn(4,4′-dimethyl-2,2′-bipyridine)(CO)₃Br]
  参考文献：
  名称：

  Amino acid bioconjugation via iClick reaction of an oxanorbornadiene-masked alkyne with a Mn^I(bpy)(CO)₃-coordinated azide

  摘要：

  无催化剂室温iClick反应中，非对称性2,3-二取代的氧合降冰片二烯（OND）作为“隐匿”的炔烃类似物与[Mn(N3)(bpyCH3,CH3)(CO)3]反应，得到了苯丙氨酸酯生物偶联物，其中模型氨基酸通过环加成-逆-狄尔斯-阿尔德（crDA）反应序列中形成的三唑配体与金属部分相连，这是基于金属中心反应性的生物正交偶联反应的一种新方法。

  DOI：

  10.1039/c4cc07892f

文献信息

• Spectroscopic (IR, UVVis, 1H and 119Sn NMR, resonance raman) properties of [(C6H5)3EM(CO)3(α-diimine)] (M = Mn, E = Ge, Sn, Pb; M = Re, E = Sn) complexes and x-ray structure of [(C6H5)3SnMn(CO)3(t-Bu-DAB)]
  作者：Ronald R. Andréa、Wim G.J. De Lange、Derk J. Stufkens、Ad Oskam

  DOI：10.1016/s0020-1693(00)90570-x

  日期：1988.9

  70(1) A and the two MnN bond lengths are 2.10(2) A. Infrared (IR), electronic absorption, 1 H and 119 Sn NMR and resonance Raman (rR) spectra are reported for the complexes [(C 6 H 5 ) 3 EM(CO) 3 (α-diimine)] (M = Mn, E = Ge, Sn, Pb; M = Re, E = Sn; α-diimine = 1,4-diaza-1,3-butadiene, pyridine-2-carbaldehyde-imine and 2,2′-bipyridine). The IR bands in the CO stretching region are assigned and the rR effect

  摘要采用重原子法确定了标题化合物的X射线结构，并通过对4598次独立反射的块对角最小二乘法计算，对其进行了精化。晶体是单斜晶体，空间群P 2 1 / c，晶胞尺寸为a = 20.025（1），b = 18.917（1），c = 17.117（1）A，β= 112.120（0）°和Z = 8。该络合物在Mn原子周围具有接近八面体的几何形状。MnSn键长为2.70（1）A，两个MnN键长为2.10（2）A。据报道红外（IR），电子吸收，1 H和119 Sn NMR和共振拉曼（rR）光谱对于络合物[（C 6 H 5）3 EM（CO）3（α-diimine）]（M = Mn，E = Ge，Sn，Pb; M = Re，E = Sn;α-diimine= 1,4 -二氮杂-1,3-丁二烯，吡啶-2-甲醛-亚胺和2,2'-联吡啶）。
• Photoinduced in Vivo Magnetic Resonance Imaging (MRI) with Rapid CO Release from an MnCO‐Protein Needle Composite
  作者：Fuminori Hyodo、Takeya Sho、Basudev Maity、Kenta Fujita、Yoko Tachibana、Satoko Akashi、Megumi Mano、Yuki Hishikawa、Masayuki Matsuo、Takafumi Ueno

  DOI：10.1002/chem.201802445

  日期：2018.8.9

  Construction of an artificial protein needle (PN), which includes the membrane puncturing needle domain of bacteriophage T4 conjugated to Mn carbonyl (MnCO) complexes, is reported. The responsiveness to visible light of the MnCO complex makes it useful as a photoinduced in vivo magnetic resonance imaging contrast reagent (MRI CR), because the PN carrier has the potential to deliver the MnCO complex into mouse

  报道了一种人工蛋白针（PN）的构建，该蛋白包括与Mn羰基（MnC​​O）复合物结合的噬菌体T4的膜穿刺针结构域。MnCO配合物对可见光的响应性使其可用作光诱导的体内磁共振成像造影剂（MRI CR），因为PN载体具有将MnCO配合物递送到小鼠肿瘤中的潜力，并保留了体内的协调结构。体内环境。此外，与相应的MnCO配合物相比，该复合材料作为MRI CR具有更高的弛豫性和更长的循环时间。这些结果证明通过使用人工金属蛋白构建响应性的体内MRI CR。
• Photochemistry of metal—metal bonded complexes
  作者：Maarten W. Kokkes、Wim G.J. De Lange、Derk J. Stufkens、Ad Oskam

  DOI：10.1016/0022-328x(85)88053-0

  日期：1985.10

  Complexes op the type (CO)5MM′(CO)3(α-diimme) (M, M′ = Mn, Re) were photolyzed in 2-Me-THF at 293 K in the absence and presence of PR3 by irradiation in the low energy M′ → α-diimine charge transfer band. In most cases the primary photoprocess appeared to be homolysis of the (M-M′) metal—metal bond. In the absence of PR3 the radicals formed react with each other to give M2(CO)10 and M′2(CO)6(α-diimine)2. It

  络合物运算类型（CO）5 MM'（CO）3（α-diiMMe）（M，M'=的Mn，Re）的分别在293K在不存在和PR的存在光分解在2-ME-THF 3通过照射在低能M'→α-二亚胺电荷转移带中。在大多数情况下，主要的光处理似乎是（MM'）金属-金属键的均相溶解。在没有PR的3形成的基团相互反应，得到中号2（CO）10和M' 2（CO）6（α-二亚胺）2。结果表明，这些M'的稳定性2（CO）6（α-二亚胺）2个配合物依赖于α二亚胺配体使用。
• Interrogating heterobimetallic co-catalytic responses for the electrocatalytic reduction of CO₂ using supramolecular assembly
  作者：Charles W. Machan、Clifford P. Kubiak

  DOI：10.1039/c6dt01956k

  日期：——

  The use of hydrogen-bonding interactions to direct the non-covalent assembly of a heterobimetallic supramolecular system with Re and Mn bipyridine-based electrocatalysts is reported. Under catalytic conditions, the formation of hydrogen bonds generates a catalyst system which passes ∼10% more current than the individual current responses of the respective Re and Mn complexes for the reduction of CO2

  据报道，使用氢键相互作用来指导异双金属超分子系统与基于Re和Mn联吡啶的电催化剂的非共价组装。在催化条件下，氢键的形成产生了一种催化剂体系，该体系比相应的Re和Mn配合物的电流响应高出约10％，用于将CO 2还原为CO和H 2O.红外光谱电化学研究表明，Re和Mn金属中心在还原机理中相互作用，甚至在没有底物的情况下在还原条件下形成异双金属键。这些发现表明，非共价组装是一种强大的方法，可用于生成新的助催化剂体系，该体系具有更高的反应性和转化效率。
• Steric Effects on CO₂ Reduction with Substituted Mn(bpy)(CO)₃X-Type Catalysts on Multiwalled Carbon Nanotubes Reveal Critical Mechanistic Details
  作者：Emile E. DeLuca、Thomas Chan、James M. Taylor、Byunghoon Lee、Rajiv Ramanujam Prabhakar、Clifford P. Kubiak

  DOI：10.1021/acscatal.3c05771

  日期：2024.2.2

  A series of Mn(bpy-R)(CO)3Br (bpy-R = 4,4′-R-2,2′-bipyridine) complexes with systematic substituent variations (R = H, –Me, –Et, tBu, and –Ph) are immobilized on multiwalled carbon nanotubes (MWCNTs) and investigated as electrocatalysts for CO2 reduction to study substituent effects on heterogenized molecular electrocatalysis. The electrochemical response and catalytic activity of each heterogenized

  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