Rh(TCPPCO₂Me)Cl | 1142922-87-9

• 英文名称: Rh(TCPPCO₂Me)Cl
• 英文别名: [5,10,15,20-tetrakis(4-methoxycarbonylphenyl)porphyrinato]Rh(III) chloride
• CAS: 1142922-87-9
• 化学式: C₅₂H₃₆ClN₄O₈Rh
• 分子量: 983.238
• InChiKey: XEKFSBMXJLUYFR-HTMHXADGSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.73
• 重原子数：
  66.0
• 可旋转键数：
  8.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  159.18
• 氢给体数：
  0.0
• 氢受体数：
  10.0

文献信息

• Network topology and cavity confinement-controlled diastereoselectivity in cyclopropanation reactions catalyzed by porphyrin-based MOFs
  作者：Konstantin Epp、Bart Bueken、Benjamin J. Hofmann、Mirza Cokoja、Karina Hemmer、Dirk De Vos、Roland A. Fischer

  DOI：10.1039/c9cy00893d

  日期：——

  that the stereoselectivity of a reaction can be controlled by directing groups of substrates, by network topology and by local cavity confinement of metal–organic framework (MOF) catalysts. We applied the porphyrin-based PCN-224(Rh), which contains no stereocenters in the cyclopropanation reaction using ethyl diazoacetate (EDA) as carbene source. When styrene and other non-coordinating olefins are used

  在这项工作中，我们表明，可以通过引导底物组，网络拓扑结构和金属-有机骨架（MOF）催化剂的局部腔约束来控制反应的立体选择性。我们使用了基于卟啉的PCN-224（Rh），该化合物在使用重氮乙酸乙酯（EDA）作为卡宾源的环丙烷化反应中不包含立体中心。当苯乙烯和其他非配位烯烃用作底物时，活性高，但未观察到非对映选择性。有趣的是，4-氨基-和4-羟基苯乙烯底物的转化以高达23：1（反式 ： 顺式）的高非对映异构体比率（dr）发生）。我们将其归因于由于底物与邻近的Rh中心的底物配位而导致的局部孔限制效应，后者将烯烃相对于活性位点定位，从而破坏了配位底物的局部对称性。通过使用PCN-222（Rh）作为催化剂可以改善局部孔隙的限制，这是PCN-224（Rh）的结构类似物，具有特征性的Kagomé拓扑结构，具有较短的Rh-Rh距离。出色的博士42：1（反 ： 顺观察到4-氨基苯乙烯。在这种情况下，底物的长
• Effects of p-substituents on electrochemical COoxidation by Rh porphyrin-based catalysts
  作者：Shin-ichi Yamazaki、Yusuke Yamada、Sahori Takeda、Midori Goto、Tsutomu Ioroi、Zyun Siroma、Kazuaki Yasuda

  DOI：10.1039/b925413g

  日期：——

  Electrochemical CO oxidation by several carbon-supported rhodium tetraphenylporphyrins with systematically varied meso-substituents was investigated. A quantitative analysis revealed that the p-substituents on the meso-phenyl groups significantly affected CO oxidation activity. The electrocatalytic reaction was characterized in detail based on the spectroscopic and X-ray structural results as well as electrochemical analyses. The difference in the activity among Rh pophyrins is discussed in terms of the properties of p-substituents along with a proposed reaction mechanism. Rhodium tetrakis(4-carboxyphenyl)porphyrin (Rh(TCPP)), which exhibited the highest activity among the porphyrins tested, oxidized CO at a high rate at much lower potentials (<0.1 V vs. a reversible hydrogen electrode, at 60 °C) than the present PtRu catalysts. This means that CO is electrochemically oxidized by this catalyst when a slight overpotential is applied during the operation of a proton exchange membrane fuel cell. This catalyst exhibited little H2 oxidation activity, in contrast to Pt-based catalysts.

  研究了几种碳支撑的四苯基卟啉铑对 CO 的电化学氧化作用。定量分析显示，介苯基上的 p 取代基对 CO 氧化活性有显著影响。根据光谱和 X 射线结构结果以及电化学分析，对该电催化反应进行了详细表征。本文从对取代基的性质和反应机理的角度讨论了 Rh 罂粟碱之间的活性差异。与现有的铂钌催化剂相比，四(4-羧基苯基)卟啉铑（Rh(TCPP)）在测试的卟啉中表现出最高的活性，能在更低的电位下（与可逆氢电极相比，在 60 °C，<0.1 V）高速氧化 CO。这意味着在质子交换膜燃料电池的运行过程中，当施加轻微的过电位时，CO 就会被这种催化剂电化学氧化。与基于铂的催化剂相比，这种催化剂几乎没有 H2 氧化活性。
• Ultrathin two-dimensional porphyrinic metal-organic framework nanosheets induced by the axial aryl substituent
  作者：Jurong Dong、Yufei Wang、Yu-Lin Lu、Li Zhang

  DOI：10.1016/j.cclet.2022.108052

  日期：2022.12

  Ultrathin two-dimensional metal-organic framework nanosheets have emerged as a promising kind of heterogeneous catalysts. Herein, we report a new kind of 2D porphyrinic metal-organic framework nanosheets of Rh2-PCN-222, which was prepared from the self-assembly of the metalloporphyrin ligand Rh(TCPP)(DCB) (TCPP = 5,10,15,20-tetrakis(4-methoxycarbonylphenyl)porphyrin; DCB = 3,4-dichlorobenzene) and

  超薄二维金属有机骨架纳米片已成为一种很有前途的多相催化剂。在此，我们报道了一种新型二维卟啉金属有机骨架纳米片 Rh2-PCN-222，它是由金属卟啉配体 Rh(TCPP)( DCB) (TCPP = 5,10,15, 20-四(4-甲氧基羰基苯基)卟啉；DCB = 3,4-二氯苯)和ZrCl4在两种单羧酸存在下作为调节剂。Rh2-PCN-222 纳米片的厚度表征为原子力显微镜 (AFM) 测定为 5.4-9.6 nm。研究发现，控制 MOF 各向异性生长的轴向芳基二氯苯基取代基对于纳米片的形成至关重要。催化结果表明，Rh2-PCN-222纳米片对CO 2转化是有效的。
• Stereo-controlled cyclopropanation catalysis within the confined pores of porphyrin MOFs
  作者：Karina Hemmer、Raphael Bühler、Martin Elsner、Mirza Cokoja、Roland A. Fischer

  DOI：10.1039/d2cy02144g

  日期：——

  Three Rh-porphyrin MOF catalysts show a MOF topology independent stereoselectivity enhancement for styrene derivatives with coordinating functionalities. Upon donor molecule addition, the activity is increased facilitating Rh-carbene formation.

  三种 Rh-卟啉 MOF 催化剂显示出 MOF 拓扑与配位官能团无关，可提高苯乙烯衍生物的立体选择性。添加供体分子后，活性会提高，从而促进 Rh-羰基的形成。
• Site‐Isolated Rhodium(II) Metalloradicals Catalyze Olefin Hydrofunctionalization
  作者：Zihang Qiu、Hao Deng、Constanze N. Neumann

  DOI：10.1002/anie.202401375

  日期：2024.4.24

  Heterogenization of Rh(II) porphyrin catalysts in a metal–organic framework is crucial for catalyst turnover in thermal olefin hydrosilylation and hydrogermylation. Unlike MOF-supported metalloradical catalysts, homogeneous analogues convert to closed shell species that obstruct catalytic turnover. Site-isolated Rh(II) metalloradicals are readily accessed via MOF synthesis with a linker containing

  金属有机骨架中 Rh(II) 卟啉催化剂的多相化对于热烯烃氢化硅烷化和氢甲酰化中的催化剂周转至关重要。与 MOF 支持的金属自由基催化剂不同，均相类似物会转化为阻碍催化周转的闭壳物质。位点隔离的 Rh(II) 金属自由基可以通过含有金属烷基键的连接基的 MOF 合成，然后进行 Rh−C 光解来轻松获得。