zinc(II)-5,10,15-trimesitylphenyl-20-(4’,4’,5’,5’-tetramethly-[1’,3’,2’]dioxaborolan-2’-yl)porphyrin | 499219-41-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: zinc(II)-5,10,15-trimesitylphenyl-20-(4’,4’,5’,5’-tetramethly-[1’,3’,2’]dioxaborolan-2’-yl)porphyrin
• CAS: 499219-41-9
• 化学式: C₅₃H₅₃BN₄O₂Zn
• 分子量: 854.23
• InChiKey: AZOSQAMCAYKPAQ-XSQOKGTOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.99
• 重原子数：
  61.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  72.44
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  4,6-二碘二苯并呋喃 、 zinc(II)-5,10,15-trimesitylphenyl-20-(4’,4’,5’,5’-tetramethly-[1’,3’,2’]dioxaborolan-2’-yl)porphyrin 在 potassium phosphate 、 四(三苯基膦)钯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 以14%的产率得到4,6-bis[5-(10,15,20-trimesitylporphyrinyl)]dibenzofuran
  参考文献：
  名称：

  锰卟啉以水为氧源对底物进行催化电子转移氧化

  摘要：

  锰（V）-羰基卟啉是通过在乙腈中用三（2,2'-联吡啶）钌（III）（[Ru（bpy）3 ] 3+ ; 2当量）进行电子转移氧化制得的（CH 3 CN）含有水。锰卟啉的电子转移氧化速率常数已根据马库斯电子转移理论进行了测定和评估。将[Ru（bpy）3 ] 3+加入到烯烃（苯乙烯和环己烯）的CH 3溶液中在催化量的锰-卟啉存在下，含CN的水可有效地提供环氧化物，二醇和醛。环氧化合物通过水解转化为相应的二醇，然后进一步氧化为相应的醛。由于所用的锰-卟啉的氧化电位和配体的空间体积不同，其周转数也有很大差异。乙苯还使用锰卟啉作为电子转移催化剂被氧化成1-苯乙醇。通过使用18确定底物氧合中的氧源为水O标记的水。在单周转条件下，通过监测与环己烯反应中产生的锰（III）物种引起的吸光度增加，直接确定了锰（V）-氧代物种与环己烯的反应速率常数。研究表明，环己烯催化电子转移氧化的速率决定步骤是电子从[Ru（bpy）3

  DOI：

  10.1002/chem.201202041

文献信息

• Catalytic O−O Activation Chemistry Mediated by Iron Hangman Porphyrins with a Wide Range of Proton-Donating Abilities
  作者：Leng Leng Chng、Christopher J. Chang、Daniel G. Nocera

  DOI：10.1021/ol034581j

  日期：2003.7.1

  [reaction: see text] A library of hanging porphyrin xanthene (HPX) compounds containing pendant groups with various proton-donating abilities (pK(a) ranging from approximately 2 to 25) has been synthesized. Their corresponding chloroiron(III) complexes promote the catalase-like disproportionation of hydrogen peroxide. The overall activity and turnover numbers (TONs) are maximal for iron HPX complexes

  [反应：见正文]已合成了一个含卟啉x吨（HPX）化合物的悬挂化合物库，该化合物包含具有各种质子给体能力（pK（a）约为2至25）的侧基。它们相应的氯铁（III）配合物可促进过氧化氢类似过氧化氢酶的歧化反应。对于带有酸性氢键悬垂物的铁HPX络合物，总活性和周转率（TONs）最大。这些结果表明，对分子内质子存量的仔细控制可以显着影响OO键的催化活化。
• Towards the synthesis of substituted porphyrins by a pyridyl group bearing a reactive functionality
  作者：Maya El Ojaimi、Benoit Habermeyer、Claude P. Gros、Jean-Michel Barbe

  DOI：10.1142/s108842461000232x

  日期：2010.6

  Pyridyl-substituted porphyrins bearing a reactive functionality were prepared via Suzuki cross-coupling reactions and resulted in very good yields. These compounds are precursors of new porphyrin architectures able to coordinate two metals: one in the porphyrin core and the second around the pyridyl moiety. During the coupling reactions, a higher reactivity of a chloro picolyl group was evidenced compared to a bromo function on the same reacting molecule.

  通过铃木交叉偶联反应制备了具有活性官能团的吡啶基取代卟啉，并获得了非常高的产率。这些化合物是新卟啉结构的前体，能够配位两种金属：一种在卟啉核心，另一种在吡啶基周围。在偶联反应过程中，与同一反应分子上的溴功能相比，氯吡啶基的反应活性更高。
• Synthesis and Photophysical Properties of Two Diazaporphyrin–Porphyrin Hetero Dimers in Polar and Nonpolar Solutions
  作者：Fawzi Abou-Chahine、Daisuke Fujii、Hiroshi Imahori、Haruyuki Nakano、Nikolai V. Tkachenko、Yoshihiro Matano、Helge Lemmetyinen

  DOI：10.1021/jp510903a

  日期：2015.6.18

  Two diazaporphyrin (DAP)-porphyrin hetero dimers, in beta-meso and beta-beta configurations, were prepared to study their photoinduced intramolecular electron transfer properties. The two meso nitrogen atoms in the porphyrin ring of DAP change its redox potential, making DAP more easily reduced, compared to its porphyrin counterpart. A charge-transfer from porphyrin to DAP in both hetero dimers was verified by versatile optical spectroscopic methods. The steady-state fluorescence spectra indicated an efficient intramolecular exciplex formation for both dimers. For the beta-meso dimer, ultrafast time-resolved spectroscopic methods revealed the subpicosecond formation of two types of primary short-living (1-18 ps) intramolecular exciplexes, which relaxed in toluene to form a long-living final exciplex (1.4 ns) followed by a longer-living charge transfer complex (>5 ns). However, in benzonitrile, the lifetime of the final exciplex was longer (660 ps) as was that of the charge transfer complex (180 ps). The beta-beta analogue formed similar short-living exciplexes in both solvents, but the final exciplex and the charge transfer state had significantly shorter lifetimes. The electrochemical redox potential measurements and density functional theory calculations supported the proposed mechanism.