[Rh(5,10,15,20-tetratolylporphyrin)CH2CH2Ph] | 252868-55-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Rh(5,10,15,20-tetratolylporphyrin)CH2CH2Ph]
• 英文别名: [Rh(5,10,15,20-tetratolylporphyrin)CH₂CH₂Ph]；Rh^III(ttp)CH₂CH_2Ph；rhodium(III)(5,10,15,20-tetratolylporphyrinato dianion)CH₂CH_2Ph；Rh(tpp)CH2CH2Ph；Rh(ttp)CH2CH2Ph；Rh(5,10,15,20-tetratolylporphyrinato)CH2CH2Ph
• CAS: 252868-55-6
• 化学式: C₅₆H₄₅N₄Rh
• 分子量: 876.906
• InChiKey: HVDXXAXLNILNER-HTMHXADGSA-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：

  [Rh(5,10,15,20-tetratolylporphyrin)CH2CH2Ph] 在 2,2,6,6-tetramethylpiperidinoxy 作用下， 以 氘代苯 为溶剂， 生成 Rh(ttp)Me
  参考文献：
  名称：

  Nonradical Trapping Pathway for Reactions of Nitroxides with Rhodium Porphyrin Alkyls Bearing β-Hydrogens and Subsequent Carbon−Carbon Bond Activation

  摘要：

  A novel nitroxide-induced hydrogen atom abstraction and beta-elimination of rhodium porphyrin alkyls has been observed. Subsequent carbon-carbon bond activation of methyl-substituted nitroxides by the rhodium(II) porphyrin radical yielded rhodium porphyrin methyl complexes.

  DOI：

  10.1021/om0201718
• 作为产物：
  描述：

  苯乙烯 、 Rh(5,10,15,20-tetratolylporphyrinato)(β-N-pyrrolidonylethyl) 以 氘代苯 为溶剂， 以99%的产率得到[Rh(5,10,15,20-tetratolylporphyrin)CH2CH2Ph]
  参考文献：
  名称：

  1,2-Rearrangements of β-Nitrogen-Substituted (Porphyrinato)rhodium(III) Ethyls

  摘要：

  (Porphyrinato)rhodium(III) ethyls containing beta-nitrogen substituents have been showed to undergo clean, thermal 1,2-rearrangements into the alpha-nitrogen-substituted rhodium ethyls. The rates and the equilibrium positions were found to be dependent on the electronic nature of the N substituents. Complexes 1a-3a were characterized by X-ray crystallography.

  DOI：

  10.1021/om0501475

文献信息

• Alkylation of Rhodium Porphyrin Complexes with Primary Alcohols under Basic Conditions
  作者：Yongjun Bian、Chun Meng Tam、Ching Tat To、Xingyu Qu、Kin Shing Chan

  DOI：10.1021/acs.organomet.9b00454

  日期：2019.10.14

  utilized as the alkylating reagents to conveniently access rhodium porphyrin alkyl complexes in up to 91% yields under basic conditions. Mechanistic investigations suggest two possible pathways for the C–O bond cleavage: (1) nucleophilic substitution with rhodium(I) porphyrin anion and (2) a borrowing hydrogen pathway via rhodium(III) porphyrin hydride.

  伯醇已成功地用作烷基化试剂，可在碱性条件下以高达91％的产率方便地获得铑卟啉烷基络合物。机理研究表明，C-O键断裂的两个可能途径是：（1）用铑（I）卟啉阴离子进行亲核取代，以及（2）通过铑（III）卟啉氢化物借入氢途径。
• Reactions of nitroxides with metalloporphyrin alkyls bearing beta hydrogens: Aliphatic carbon–carbon bond activation by metal centered radicals
  作者：Kin Shing Chan、Kin Wah Mak、Man Kin Tse、Siu Kwan Yeung、Bao Zhu Li、Yun Wai Chan

  DOI：10.1016/j.jorganchem.2007.11.009

  日期：2008.2

  Nitroxide-induced beta-hydrogen atom abstraction and beta-elimination of rhodium porphyrin alkyls have been observed. Rhodium(II) porphyrin radical were proposed intermediates to form first and subsequently reacted via aliphatic carbon–carbon bond activation with alkyl substituted nitroxides to yield rhodium porphyrin alkyl complexes.

  已经观察到亚硝酸盐诱导的β-氢原子提取和铑卟啉烷基的β消除。提出了铑（II）卟啉自由基的中间体，该中间体首先形成，然后通过脂族碳-碳键活化与烷基取代的氮氧化物反应，生成铑卟啉烷基络合物。