(5,10,15,20-tetra(2,4,6-trimethylphenyl)porphyrinato)rhodium(III) ethyl | 342790-12-9

• 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: (5,10,15,20-tetra(2,4,6-trimethylphenyl)porphyrinato)rhodium(III) ethyl
• 英文别名: ethyl(5,10,15,20-tetramesitylporphyrinato)rhodium(III)；Rh(tmp)Et；Rh(III)Et(5,10,15,20-tetramesitylporphyrinato)；Rh(5,10,15,20-tetramesitylporphyrinato)Et；RhEt(5,10,15,20-tetramesitylporphyrinato)；[Rh(meso-tetramesitylporphyrin)Et]
• CAS: 342790-12-9
• 化学式: C₅₈H₅₇N₄Rh
• 分子量: 913.023
• InChiKey: AKSFFBAJVSEBFN-WSJWEZPUSA-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

• 作为产物：
  描述：

  Rh(tmp)Me 以 苯 为溶剂， 生成 (5,10,15,20-tetra(2,4,6-trimethylphenyl)porphyrinato)rhodium(III) ethyl
  参考文献：
  名称：

  腈的脂族碳-碳键的金属热活化：范围和机理

  摘要：

  Rh（tmp）使用Ph 3 P作为最优化的启动子配体在130°C活化了一系列α-烷基乙腈，2-甲硅烷基乙腈和2-烷基苯甲腈的C（sp 3）-C（sp 3）键。选择性的脂肪族-脂肪族碳-碳键活化（CCA）发生在没有芳族-脂肪族或芳族-氰化物键活化的α-烷基乙腈和2-烷基苄腈上。对于2-甲硅烷基乙腈，观察到了竞争性的C-Si和C-C键活化。Rh（tmp）烷基的产率受键能和腈的位阻的影响。为碳-碳键的激活（CCA）的动力学研究吨BuCN在130℃下显示速率定律：速率= ķ ' ķ 1[Rh（tmp）]米[Ph 3 P] n+ k 3 K 2（K 1 [Ph 3 P]）/（1 + K 1 [Ph 3 P]）[Rh（tmp）] [ t BuCN]。建议在过渡状态下，CCA发生在与Rh（tmp）配比的t BuCN处，配比为1：1。

  DOI：

  10.1021/om070064j

文献信息

• Activation of aliphatic carbon–carbon bonds of esters and amides by rhodium(II) porphyrin
  作者：Lirong Zhang、Kin Shing Chan

  DOI：10.1016/j.jorganchem.2007.01.012

  日期：2007.4

  Aliphatic carbon–carbon bonds of esters and amides were activated successfully with rhodium(II) porphyrin radical to give rhodium(III) porphyrin alkyls in moderate yields.

  酯和酰胺的脂族碳-碳键已被铑（II）卟啉自由基成功激活，从而以中等收率得到了铑（III）卟啉烷基。
• Base-Promoted, Selective Aliphatic Carbon−Carbon Bond Cleavage of Ethers by Rhodium(III) Porphyrin Complexes
  作者：Tsz Ho Lai、Kin Shing Chan

  DOI：10.1021/om900270v

  日期：2009.12.28

  Base-promoted, selective aliphatic carbon(α)−carbon(β) bond activation (CCA) of ethers by (5,10,15,20-tetramesitylporphyrinato)rhodium(III) iodide was achieved.

  实现了碘化（5,10,15,20-四氢卟啉基）碘化铑（III）的碱促进的选择性脂肪族碳（α）-碳（β）键活化（CCA）。
• Activation of unstrained aliphatic carbon–carbon bonds by a transition metal complex
  作者：Man Kin Tse、Kin Shing Chan

  DOI：10.1039/b100501o

  日期：——

  The first examples of intermolecular activation of aliphatic carbon–carbon bonds by transition metal complexes are demonstrated in the reaction of nitroxides with a rhodium(II) porphyrin radical.

  分子间的第一个例子 激活氮氧化物与铑（II）卟啉自由基的反应证明了过渡金属配合物能形成脂族碳-碳键。
• Aliphatic Carbon−Carbon Bond Activation of Nitriles by Rhodium(II) Porphyrin
  作者：Kin Shing Chan、Xin Zhu Li、Chun Wah Fung、Lirong Zhang

  DOI：10.1021/om060828f

  日期：2007.1.1

  The aliphatic C(alpha)-C(beta) bonds of a series of nitriles were activated by Rh(tmp) using Ph3P as the promoting ligand from 100 to 130 degrees C. Kinetic studies at 130 degrees C revealed the rate law, rate = k'K-1[Rh(tmp)][Ph3P](n) + k(3)K(2)(K-1[Ph3P])/(1 + K-1[Ph3P])[Rh(tmp)][(BuCN)-Bu-t] and suggested the carbon-carbon bond activation occurred at the coordinated (BuCN)-Bu-t with Rh(tmp) in a 1:1 ratio in the transition state.
• Room-Temperature Selective Aliphatic Carbon–Carbon Bond Activation and Functionalization of Ethers by Rhodium(II) Porphyrin
  作者：Siu Yin Lee、Tsz Ho Lai、Kwong Shing Choi、Kin Shing Chan

  DOI：10.1021/om200280w

  日期：2011.7.25

  Selective aliphatic carbon(alpha)-carbon(beta) bond activation of ethers by (5,10,15,20-tetramesitylporphyrinato)rhodium (II) (Rh(tmp) (1)) was achieved at room temperature to yield corresponding rhodium porphyrin alkyls and the functionalized esters. Rh(tmp)OH was the proposed intermediate responsible for cleaving the C(alpha)-C(beta) bond. The reaction is general for both straight- and branch-chain ethers.