[Rh(5,10,15,20-tetratolylporphyrinato)(COPh)] | 874299-58-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: [Rh(5,10,15,20-tetratolylporphyrinato)(COPh)]
• 英文别名: [Rh(ttp)(COPh)]；Rh(III)(5,10,15,20-tetratolylporphyrinato)COPh；(5,10,15,20-tetratolylporphyrinato)(benzoyl)rhodium(III)；Rh(ttp)COPh；[Rh(5,10,15,20-tetrakis-4-tolylporphyrinato)(COPh)]
• CAS: 874299-58-8
• 化学式: C₅₅H₄₁N₄ORh
• 分子量: 876.862
• InChiKey: SQMKVRAHAWCGFD-HTMHXADGSA-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：
  None
• 环数：
  None
• 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

• 作为产物：
  描述：

  Rh(ttp)CH2COPh 反应 168.0h， 以99%的产率得到[Rh(5,10,15,20-tetratolylporphyrinato)(COPh)]
  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

文献信息

• Mild and Selective C(CO)–C(α) Bond Cleavage of Ketones by Rhodium(III) Porphyrins: Scope and Mechanism
  作者：Hong Sang Fung、Bao Zhu Li、Kin Shing Chan

  DOI：10.1021/om200788p

  日期：2012.1.23

  Rhodium(III) porphyrins were found to undergo selective C(CO)–C(α) bond activation (CCA) of ketones promoted by water at temperatures as low as 50 °C. The acyl group of the ketone was transferred to the rhodium center, and the alkyl fragment was oxidized to a carbonyl moiety accordingly. The hydroxyl group of water is transferred to the rhodium porphyrin through hydrolysis of the kinetic α-carbon–hydrogen

  发现铑（III）卟啉在低至50°C的温度下会受到水促进的酮的选择性C（CO）–C（α）键活化（CCA）。酮的酰基转移到铑中心，并且烷基片段相应地氧化成羰基部分。水的羟基通过动力学α-碳-氢键活化（α-CHA）产物的水解转移到卟啉铑上，得到Rh III（ttp）OH（ttp = 5,10,15,20-四甲苯基卟啉二价阴离子） ），然后裂解酮的C（CO）–C（α）键。
• Activation of Aldehydic Carbon−Hydrogen Bonds under Aerobic Conditions by Masked Rhodium(III) Porphyrin Cation
  作者：Kin Shing Chan、Cheuk Man Lau、Siu Kwan Yeung、Tsz Ho Lai

  DOI：10.1021/om070135e

  日期：2007.4.1

  RhIII(ttp)CH2CH2OH activated the aldehydic carbon−hydrogen bonds of functionalized aryl and enolizable aldehydes to give high yields of Rh(ttp)COR at 50 °C under both anaerobic and aerobic conditions. The Rh(ttp)(C2H4)OH intermediate was proposed to form via β-hydroxy elimination. The reactions exhibited rate and yield enhancement upon the addition of Ph3P, suggesting ligand-promoted β-elimination

  Rh III（ttp）CH 2 CH 2 OH活化了功能化芳基和可烯化醛的醛碳氢键，在厌氧和有氧条件下，在50°C时，均具有高产率的Rh（ttp）COR。提出通过β-羟基消除形成Rh（ttp）（C 2 H 4）OH中间体。加入Ph 3 P时，反应显示出速率和产率提高，表明配体促进了β消除。Hammett图的非线性自由能关系表明，取决于芳基醛对位取代基的电子效应，速率决定步骤（结合或活化）的多步反应。
• Acylation of Rhodium(III) Porphyrin Complexes with Carboxylic Acids: Scope and Mechanism
  作者：Ho Yin Yu、Hung Kay Lee、Kin Shing Chan

  DOI：10.1021/acs.organomet.1c00457

  日期：2021.11.22

  Rhodium(III) porphyrin complexes undergo C(═O)–O bond activation (COA) of carboxylic acids to give the corresponding rhodium(III) porphyrin acyl complexes RhIII(ttp)COR up to 90% yield. Mechanistic studies suggested either a σ-bond metathesis reaction or 1,2-addition between an active rhodium(III) porphyrin hydride species, RhIII(ttp)–H, and the carboxylic acid (R(C═O)–OH) to give the corresponding

  铑 (III) 卟啉配合物经过羧酸的 C(=O)-O 键活化 (COA)，得到相应的铑 (III) 卟啉酰基配合物 Rh III (ttp)COR，产率高达 90%。机理研究表明活性铑 (III) 卟啉氢化物 Rh III (ttp)-H 和羧酸 (R(C=O)-OH)之间的 σ 键复分解反应或 1,2-加成反应给出相应的 Rh III (ttp)COR 产物。
• Mild and Selective C(CO)–C(α) Bond Activation of Ketones with Rhodium(III) Porphyrin β-Hydroxyethyl
  作者：Chung Sum Chan、Siu Yin Lee、Kin Shing Chan

  DOI：10.1021/om3009519

  日期：2013.1.14

  Rhodium(III) porphyrin beta-hydroxyethyl, Rh-III(ttp)CH2CH2OH (ttp = 5,10,15,20-tetratolylporphyrinato dianion), was found to serve as a precursor of the highly reactive Rh-III(ttp)OH for the C(CO)-C(alpha) bond activation (CCA) of ketones under mild and aerobic conditions of 25-50 degrees C.