Ru(5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin)(O)₂ | 142718-07-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: Ru(5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin)(O)₂
• 英文别名: (5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato)(dioxo)ruthenium(VI)；dioxo-ruthenium(VI) tetrakis(2,6-dichlorophenyl)porphyrin complex；dioxo(tetrakis(2,6-dichlorophenyl)porphyrinato)ruthenium(VI)；[Ru^VI(5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato)(O)₂]；[Ru^VI(TDCPP)(O)₂]；[RuVI(2,6-Cl2tpp)O2]；Ru(VI)(TDCPP)O2
• CAS: 142718-07-8
• 化学式: C₄₄H₂₀Cl₈N₄O₂Ru
• 分子量: 1021.36
• InChiKey: LJEIPXWJDHOHPQ-CXJMORQYSA-N

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：

  Ru(5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin)(O)₂ 在 三甲基氯硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以90%的产率得到dichlororuthenium(IV) meso-tetrakis(2,6-dichlorophenyl)porphyrin
  参考文献：
  名称：

  温和的催化氧化系统：卟啉钌和2,6-二氯吡啶N-氧化物用于烯烃二羟基化

  摘要：

  通过使用二氯钌（IV）内消旋-四（2,6-二氯苯基）卟啉[Ru（IV）（TDCPP）以Cl 2 ]为催化剂，以2,6-二氯吡啶N-氧化物（Cl 2 pyNO）为氧化剂，其中通过“一锅法”反应以中等收率得到1,2-二醇。

  DOI：

  10.1002/adsc.201000455
• 作为产物：
  描述：

  [Ru(2,6-Cl₂tpp)Cl₂] 在 air 、 碳酸氢钠 作用下， 以 氘代氯仿 、 水 为溶剂， 反应 12.0h， 以10%的产率得到Ru(5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin)(O)₂
  参考文献：
  名称：

  通过串联环氧化-异构化途径，钌卟啉催化将末端芳基烯烃有氧氧化为醛。

  摘要：

  DOI：

  10.1002/anie.200801500
• 作为试剂：
  描述：

  (Z)-styrene-β-d 在 吡唑 、 Ru(5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin)(O)₂ 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 cis-β-deuterio-styrene oxide 、 cis-β-deuterio-styrene oxide
  参考文献：
  名称：

  A Mechanistic Investigation of Alkene Epoxidation by Sterically Encumbered trans-Dioxoruthenium(VI) Porphyrins

  摘要：

  The highly substituted dioxoruthenium(VI) porphyrins [Ru-VI(DPP)O-2] (1a; H2DPP = 2,3,5,7,8;10,- 12,13,15,17, 18,20-dodecaphenylporphyrin), [Ru-VI(TDCPP)O-2] (Ib; H2TDCPP = meso-tetrakis(2,6- dichlorophenyl)porphyrin), and [Ru-VI(TMOPP)O-2] (1c; H2TMOPP = meso-tetrakis(2,4,6-trimethoxyphenyl)porphyrin) are competent oxidants for alkene epoxidation. The oxidations were carried out in a CH2Cl2/Hpz solution, and a paramagnetic bis(pyrazolato)ruthenium(IV) porphyrin, [Ru-IV(Por)-(pz)(2)] (2; H(2)Por = H2DPP, H2TDCPP, H2TMOPP), was isolated and characterized. For the oxidation of cis-alkenes, stereoselectivity is dependent upon both the alkenes and the ruthenium oxidants, and it decreases in the order: cis-stilbene > cis-beta-methylstyrene > cis-beta-deuteriostyrene. The observation of inverse secondary KIE for the oxidation of beta-d(2)-styrene [k(H)/k(D) = 0.87 (1a); 0.86 (1b)] but not for the alpha-deuteriostyrene oxidations suggests that the C-O bond formation is more advanced at the C(beta) atom than at the C(alpha) atom of styrene, consistent with a nonconcerted mechanism. By consideration of spin delocalization and polar effects, the second-order rate constants for the oxidation of para-substituted styrenes by complexes la-c can linearly correlate with the carboradical substituent constants sigma(mb) and sigma(JJ)(.) (Jiang, X.-K. Acc. Chem. Res. 1997, 30, 283). This implies that the styrene oxidation by the dioxoruthenium(VI) porphyrins should involve rate-limiting generation of a benzylic radical intermediate, and the magnitude of \rho(JJ)(.)\rho(mb)\ > 1 suggests that the spin delocalization effect is more important than the polar effect in the epoxidation reactions. The spontaneous epoxidation of trans-beta-methylstyrene by the sterically encumbered [Ru-VI(TDCPP)O-2] and [Ru-VI(TMOPP)O-2] complexes and the comparable Delta S-double dagger values for their reactions with trans-beta-methylstyrene and styrene are incompatible with the "side-on approach" model; a "head-on approach" model is implicated.

  DOI：

  10.1021/jo990517x

文献信息

• Arylruthenium(III) Porphyrin-Catalyzed C–H Oxidation and Epoxidation at Room Temperature and [Ru^V(Por)(O)(Ph)] Intermediate by Spectroscopic Analysis and Density Functional Theory Calculations
  作者：Ka-Pan Shing、Bei Cao、Yungen Liu、Hung Kay Lee、Ming-De Li、David Lee Phillips、Xiao-Yong Chang、Chi-Ming Che

  DOI：10.1021/jacs.8b04470

  日期：2018.6.6

  metal catalysts for efficient oxidation of hydrocarbons and identification of the reactive intermediates in the oxidation catalysis are long-standing challenges. In the rapid hydrocarbon oxidation catalyzed by ruthenium(IV) and -(III) porphyrins, the putative Ru(V)-oxo intermediates remain elusive. Herein we report that arylruthenium(III) porphyrins are highly active catalysts for hydrocarbon oxidation

  开发用于烃类有效氧化的高活性和选择性金属催化剂以及氧化催化中反应中间体的鉴定是长期存在的挑战。在钌 (IV) 和 -(III) 卟啉催化的快速烃氧化中，推定的 Ru(V)-氧代中间体仍然难以捉摸。在此我们报告芳基钌 (III) 卟啉是烃氧化的高活性催化剂。使用催化剂 [RuIII(TDCPP)(Ph)(OEt2)] (H2TDCPP = 5,10,15,20-四(2,6-二氯苯基)卟啉)，在氧化剂 m-CPBA 下氧化各种碳氢化合物的 CH 键室温下，醇/酮在 1 小时内的收率高达 99%；使用 [ nBu4N]IO4 作为温和的替代氧化剂避免了 CH 氧化中环酮形成内酯，催化环氧化反应在 5 分钟内完成，收率高达 99%，选择性高（无醛类副产物）。UV-vis、电喷雾电离质谱、共振拉曼、电子顺磁共振、动力学测量和密度泛函理论计算为 Ru(V)-氧代中间体 [RuV(TDCPP)(O)(Ph)]
• Ruthenium-Catalyzed Alkylation of Indoles with Tertiary Amines by Oxidation of a sp³CH Bond and Lewis Acid Catalysis
  作者：Ming-Zhong Wang、Cong-Ying Zhou、Man-Kin Wong、Chi-Ming Che

  DOI：10.1002/chem.200902387

  日期：2010.5.17

  catalysts for direct C‐3 alkylation of indoles, giving the desired products in high yields (up to 82 % based on 60–95 % substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron‐withdrawing or electron‐donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N‐arylindoles

  钌卟啉（特别是[Ru（2,6-Cl 2 tpp）CO]； tpp =四苯基卟啉）和RuCl 3可以作为氧化和/或路易斯酸催化剂，用于吲哚的直接C-3烷基化，从而以高纯度得到所需的产物收率（基于60–95％的底物转化率，最高可达82％）。当使用t BuOOH作为氧化剂时，这些钌化合物催化具有高区域选择性的带有吸电子或给电子取代基的各种苯胺和吲哚的氧化偶联反应，导致N-芳基吲哚烷基化为3-[[[ N -芳基-N-烷基）氨基]甲基}吲哚（收率：最高82％，转化率：最高95％）和N的烷基化-烷基或N -H吲哚成3- [对-（二烷基氨基）苄基]吲哚（收率：最高73％，转化率：最高92％）。提议涉及两个途径的暂定反应机理：可以由SP的氧化而生成的中间亚胺离子3 Ç 由oxoruthenium物种的烷基化苯胺的H键; 然后该亚胺离子可能被N-芳基吲哚捕获（途径A）或转化为甲醛，随后在路易斯的存在下，原
• Synthesis and reactivity of dihydroxoruthenium(IV) complex of tetramesitylporphyrin. Aerobic epoxidation of norbornene by ruthenium porphyrins
  作者：Wa-Hung Leung、Chi-Ming Che、Chi-Hung Yeung、Chung-Kwong Poo

  DOI：10.1016/s0277-5387(00)83049-1

  日期：1993.10

  Abstract Treatment of Ru(TMP)(CO) with m-CPBA in CH2Cl2/EtOH afforded Ru (TMP)(OH)2, isolated as air-stable violet crystals. Ru(TMP)(OH)2 in paramagnetic (μeff ca 2.7 B.M.) and displays broad 1H NMR signals with paramagnetic isotropic shifts. The IR spectrum shows a band at 760 cm−1 assignable to the RuO stretch. Ru(TMP)(OH)2 is capable of catalysing aerobic epoxidation of alkenes under mild conditions

  摘要在二氯甲烷/乙醇中用m-CPBA处理Ru（TMP）（CO），得到Ru（TMP）（OH）2，其分离为空气稳定的紫罗兰色晶体。Ru（TMP）（OH）2处于顺磁性（μeff约为2.7 BM），并显示具有顺磁性各向同性位移的宽泛1H NMR信号。红外光谱显示在760 cm-1处的谱带可归因于RuO拉伸。Ru（TMP）（OH）2能够在温和条件下催化烯烃的好氧环氧化。
• Preparation and crystal structure of trans-dihydroxo-[tetrakis(2,6-dichlorophenyl)porphinato]ruthenium(IV)·2toluene
  作者：Patrick Dubourdeaux、Manuella Tavarès、André Grand、René Ramasseul、Jean-Claude Marchon

  DOI：10.1016/0020-1693(95)04523-6

  日期：1995.12

  Abstract Trans-dihydroxo-[tetrakis(2,6-dichlorophenyl)porphinato]ruthenium(IV) ([Ru(OH)2(TDCPP)]) was prepared by meta-chloroperbenzoic acid oxidation of [Ru(CO)(TDCPP)] in dichloromethane-toluene, and its crystal structure is reported. Crystal data for [Ru(OH)2(TDCPP)]·2toluene:C44H22N4O2Cl8Ru·2C7H8, orthorhombic, space group Pbca a = 13.149(1), b = 19.893(2), c = 21.093(2)A, U = 55.17.3(2) A3, Z

  摘要通过间氯过苯甲酸氧化[Ru（CO）（TDCPP）]制备了反式-二羟基-[四（2,6-二氯苯基）卟啉]钌（IV）（[Ru（OH）2（TDCPP）]）。在二氯甲烷-甲苯中的化合物，并报道了其晶体结构。[Ru（OH）2（TDCPP）]·2甲苯：C44H22N4O2Cl8Ru·2C7H8的晶体数据，正交，空间群Pbca a = 13.149（1），b = 19.893（2），c = 21.093（2）A，U = 55.17 .3（2）A3，Z =4。轴向RuO短键距1.790（7）A在双Ru（IV）-氧键的预期范围内。两个羟基配体都大约位于两个相对的二氯苯基的平均平面上。使用2368个F> 2.5σ（F）的唯一反射对位置和热参数进行全矩阵最小二乘优化，得出R（F）= 0.063; Rw ＝ 0.066。
• Oxidation studies on mustard gas, and the first crystal structure of a metal-mustard gas complex
  作者：Nimal Rajapakse、Shahram Mehraban、Andrew Pacheco、Brian O. Patrick、Brian R. James

  DOI：10.1016/j.ica.2018.05.012

  日期：2018.10

  Attempts to selectively oxidize mustard gas [(ClCH2CH2)(2)S, abbreviated as BCES] to the non-toxic sulfoxide using a trans-Ru(TMP)(O)(2)/O-2 catalyst (TMP = porphyrin dianion of 5,10,15,20-tetramesitylporphyrin) have led to isolation and characterization, including an X-ray structure, of trans-Ru(TMP)(BCES)(2), the first such report of a metal-mustard gas complex.