Rh(tmp)Pr | 940002-36-8

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: Rh(tmp)Pr
• 英文别名: propyl(5,10,15,20-tetramesitylporphyrinato)rhodium(III)；Rh(III)(n-Pr)(5,10,15,20-tetramesitylporphyrinato)；Rh(5,10,15,20-tetramesitylporphyrinato)Pr；RhPr(5,10,15,20-tetramesitylporphyrinato)；Rh(n-Pr)(tmp)；RhPr(tmp)
• CAS: 940002-36-8
• 化学式: C₅₉H₅₉N₄Rh
• 分子量: 927.05
• InChiKey: OCJAOWYOUPWBHX-WSJWEZPUSA-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

• 作为产物：
  描述：

  (5,10,15,20-tetra(2,4,6-trimethylphenyl)porphyrinato)rhodium(III) iodide 、 二丁醚 在 KOH 作用下， 以 dibutyl ether 为溶剂， 以86%的产率得到Rh(tmp)Pr
  参考文献：
  名称：

  铑（III）卟啉配合物对以碱为基础的醚的选择性脂族碳-碳键裂解

  摘要：

  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）。

  DOI：

  10.1021/om900270v

文献信息

• Metalloradical Activations of Aliphatic Carbon−Carbon Bonds of Nitriles:  Scope and Mechanism
  作者：Kin Shing Chan、Xin Zhu Li、Lirong Zhang、Chun Wah Fung

  DOI：10.1021/om070064j

  日期：2007.5.1

  aromatic−cyanide bond activation. Competitive activations of C−Si and C−C bonds were observed for 2-silylacetonitriles. The yields of Rh(tmp) alkyls were affected by bond energy and steric hindrance of the nitriles. Kinetic studies for the carbon−carbon bond activation (CCA) of tBuCN at 130 °C revealed the rate law:  rate = k‘K1[Rh(tmp)]m[Ph3P]n + k3K2(K1[Ph3P])/(1 + K1[Ph3P])[Rh(tmp)][tBuCN]. The CCA is proposed

  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。
• 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.
• Ligand-Enhanced Aliphatic Carbon−Carbon Bond Activation of Nitroxides by Rhodium(II) Porphyrin
  作者：Kin Shing Chan、Xin Zhu Li、Siu Yin Lee

  DOI：10.1021/om1000869

  日期：2010.7.12

  Rh(tmp) underwent Ph3P-enhanced aliphatic carbon carbon bond activation with various nitroxides. (Ph3P)Rh(tmp), rapidly formed from Rh(tmp) and Ph3P, enhanced the rate, selectivity, and yield in comparison to Rh(tmp). From kinetic studies, the rate of reaction showed a first-order dependence on both Rh(tmp) and TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl) and saturation kinetics on Ph3P. The rate enhancement of (Ph3P)Rh(tmp) over Rh(tmp) was estimated to be about 11 at 70 degrees C.