Rh₂(tetra-p-tolylporphyrinato)₂ | 103533-57-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: Rh₂(tetra-p-tolylporphyrinato)₂
• 英文别名: Rh₂(ttp)₂；Rh2(ttp)2；[rhodium(II)(5,10,15,20-tetratolylporphyrin)]2；Rh2(5,10,15,20-tetrakistolylporphyrinato)2；Rh2(5,10,15,20-tetratolylporphyrinato)2；Rh(II)2(tetratolylporphyrinato(2-))2；[Rh(ttp)]2；bis[(5,10,15,20-tetra-p-tolylporphyrinato)rhodium(II)]2；[Rh(5,10,15,20-tetratolylporphyrin)]₂
• CAS: 103533-57-9
• 化学式: C₉₆H₇₂N₈Rh₂
• 分子量: 1543.49
• InChiKey: HVCFKIMRZYEJEN-SXSLMZARSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  Rh₂(tetra-p-tolylporphyrinato)₂ 、 苯乙酮 反应 0.5h， 以100%的产率得到Rh(ttp)CH2COPh
  参考文献：
  名称：

  Sterically Enhanced, Selective C(CO)−C(α) Bond Cleavage of a Ketones by Rhodium Porphyrin Methyl

  摘要：

  Selective carbon(CO) carbon(a) bond activation of ketones was achieved by rhodium(III) 5,10, 15,20-tetrakis-4-toylporphyrinato methyl (Rh(ttp)Me (1)) to yield the corresponding rhodium porphyrin acyls at temperatures as low as 50 degrees C. More hindered isopropyl ketones were much more reactive than ethyl or methyl ketones. Rh(ttp)OH(3a)was proposed to be the intermediate to cleave the C(CO)-C(alpha) bond.

  DOI：

  10.1021/om1007852
• 作为产物：
  描述：

  rhodium(III) tetrakis(4-tolyl)porphyrin chloride 在 [2.2]paracyclophane 、 KOH 、 D₂O 作用下， 以 氘代苯 为溶剂， 生成 Rh₂(tetra-p-tolylporphyrinato)₂
  参考文献：
  名称：

  Catalytic Carbon–Carbon σ-Bond Hydrogenation with Water Catalyzed by Rhodium Porphyrins

  摘要：

  The catalytic carbon carbon-cabon sigma-bond activation and hydrogenation of [2.2]paracyclophane with water in a neutral reaction medium is demonstrated. The hydrogen from water is transferred to the hydrocarbon to furnish hydrogen enrichment in good yields.

  DOI：

  10.1021/ja3047415

文献信息

• Carbon–nitrogen bond activation of amines by rhodium(III) porphyrin complexes
  作者：Ching Chi Au、Tsz Ho Lai、Kin Shing Chan

  DOI：10.1016/j.jorganchem.2010.02.007

  日期：2010.5

  Carbon–nitrogen bond activation of amines by rhodium porphyrin chloride has been achieved to give rhodium porphyrin alkyl complexes. Rhodium porphyrin hydride and rhodium porphyrin dimer were proposed as the intermediates in cleaving the C–N bond.

  已经实现了氯化卟啉铑对胺的碳-氮键活化，从而得到铑卟啉烷基络合物。提出了氢化卟啉铑和卟啉铑二聚体作为裂解C-N键的中间体。
• Reactivity Studies of Rhodium(III) Porphyrins with Methanol in Alkaline Media
  作者：Hong Sang Fung、Yun Wai Chan、Chi Wai Cheung、Kwong Shing Choi、Siu Yin Lee、Ying Ying Qian、Kin Shing Chan

  DOI：10.1021/om801029k

  日期：2009.7.27

  Rh(ttp)Cl (1a) (ttp = 5,10,15,20-tetrakistolylporphyrinato dianion) was found to react with methanol at a high temperature of 150 °C in the presence of inorganic bases to give a high yield of Rh(ttp)CH3 (2a), up to 87%. Rh(ttp)H (1d) is suggested to be the key intermediate for the carbon−oxygen bond cleavage.

  发现Rh（ttp）Cl（1a）（ttp = 5,10,15,20-四Kistolylporphyrinato二价阴离子）在无机碱存在下于150°C的高温下与甲醇反应，从而获得高产率的Rh（ ttp）CH 3（2a），高达87％。Rh（ttp）H（1d）被认为是碳-氧键裂解的关键中间体。
• Aryl carbon–chlorine (Ar–Cl) and aryl carbon–fluorine (Ar–F) bond cleavages by rhodium porphyrins
  作者：Ying Ying Qian、Man Ho Lee、Wu Yang、Kin Shing Chan

  DOI：10.1016/j.jorganchem.2015.05.039

  日期：2015.8

  been achieved with rhodium(III) tetrakis-4-tolylporphyrin chloride (Rh(ttp)Cl) to give Rh(ttp)Ar. For 4-chlorofluorobenzene, the aryl carbon–fluorine (Ar–F) bond cleavage competes with the Ar–Cl bond cleavage. Mechanistic investigations show that the Ar–Cl bond cleavage goes through metalloradical ipso-substitution mechanism, while the Ar–F bond cleavage goes through nucleophilic aromatic substitution

  芳基碳-氯（Ar-Cl）键的裂解已通过铑（III）四-4-甲苯基卟啉氯化物（Rh（ttp）Cl）生成Rh（ttp）Ar。对于4-氯氟苯，芳基碳-氟（Ar-F）键断裂与Ar-Cl键断裂竞争。机理研究表明，Ar-Cl键的裂解是通过金属铁的ipso-取代机理，而Ar-F键的裂解是通过亲核的芳族取代。可以通过调节温度和底物浓度来控制Ar-F或Ar-Cl键断裂的选择性。
• Ligand effect on the rhodium porphyrin catalyzed hydrogenation of [2.2]paracyclophane with water: key bimetallic hydrogenation
  作者：Chun Meng Tam、Ching Tat To、Kin Shing Chan

  DOI：10.1039/c7dt02002c

  日期：——

  carbon–carbon σ-bond of [2.2]paracyclophane with water has been examined with a variety of tetraarylporphyrins and axial ligands. Mechanistic investigations show that RhIII(ttp)H, which can be derived from the reaction of [RhII(ttp)]2 with water without a sacrificial reductant, plays an important role in promoting bimetallic reductive elimination to give the hydrogenation product.

  用多种四芳基卟啉和轴向配体研究了铑卟啉催化的[2.2]对环环糊精的脂族碳-碳σ键加氢反应。机理研究表明，Rh III（ttp）H可以由[Rh II（ttp）] 2与无牺牲还原剂的水反应而得，在促进双金属还原消除以提供氢化产物方面起着重要作用。
• Base-Promoted Carbon−Hydrogen Bond Activation of Alkanes with Rhodium(III) Porphyrin Complexes
  作者：Yun Wai Chan、Kin Shing Chan

  DOI：10.1021/om800397p

  日期：2008.9.22

  Base-promoted carbon−hydrogen bond activation of alkanes was achieved in the reactions of alkanes with rhodium(III) porphyrin chlorides (Rh(por)Cl) at 120 °C to give rhodium porphyrin alkyls in moderate yields. This carbon−hydrogen activation (CHA) of alkane provided a facile synthesis of Rh(por)R. Mechanistic investigation of CHA suggested that Rh(por)H and [Rh(por)]2 were key intermediates for the

  在烷烃与铑（III）卟啉氯化物（Rh（por）Cl）的反应中，烷烃的碱促进的碳氢键活化是在120°C下以中等收率得到铑卟啉烷基。烷烃的碳氢活化（CHA）提供了Rh（por）R的简便合成。CHA的机理研究表明，Rh（por）H和[Rh（por）] 2是CHA步骤的关键中间体。