Rh(5,10,15,20-tetramesitylporphyrinato)SiMe3 | 823834-99-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻唑类
• 英文名称: Rh(5,10,15,20-tetramesitylporphyrinato)SiMe3
• 英文别名: Rh(tmp)SiMe3；Rh(tetramesitylporphyrinato)(SiMe3)；[Rh(meso-tetramesitylporphyrinato)(SiMe3)]
• CAS: 823834-99-7
• 化学式: C₅₉H₆₁N₄RhSi
• 分子量: 957.151
• InChiKey: MVVOZHHQTQSJMI-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：
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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：
  None
• 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：

  (tetramesitylporphyrinato)rhodium(II) 、 三甲基氰硅烷 以 苯 为溶剂， 以16%的产率得到Rh(5,10,15,20-tetramesitylporphyrinato)SiMe3
  参考文献：
  名称：

  甲硅烷基氰化物向铑卟啉自由基的氧化加成：异氰化物或氰化物的转移机理

  摘要：

  铑卟啉自由基与吡啶配合，激活了甲硅烷基氰化物的碳-硅键，从而生成了铑卟啉甲硅烷基和氰化物。与Me 3 SiCN的反应在吡啶浓度足够高的情况下显示出二级动力学，速率= k obsd [Rh（tmp）] [Me 3 SiCN]，并且该机理被解释为涉及氰化物或异氰基转移至铑自由基。

  DOI：

  10.1021/om049253h

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。
• Mechanistic Studies of Si−CN and C−NC Bond Activation of Silylnitriles and Alkyl Isonitriles by Rhodium Porphyrin Radical:  Novel Cyanide Transfer
  作者：Lirong Zhang、Chun Wah Fung、Kin Shing Chan

  DOI：10.1021/om0605276

  日期：2006.10.1

  The Si-CN and C-NC bonds of silylnitriles and alkyl isonitriles were activated by (tetramesitylporphyrinato) rhodium(II), Rh(tmp), to give rhodium porphyrin silyls or alkyls and rhodium porphyrin cyanide, respectively. Pyridine and triphenylphosphine promoted the rates and yields of the reactions with silylnitriles, but inhibited the rates and yields of the reactions with isonitriles. The reaction of Rh( tmp) with Me3SiCN exhibited second-order kinetics (rate = k(obs)[Rh(tmp)][Me3SiCN]) at a sufficiently high concentration of pyridine. The reaction with BuNC showed fourth-order kinetics, second-order in each of the reactants; rate = k(obs)[Rh(tmp)](2)[BuNC](2). A novel cyanide transfer rate-determining step was proposed to account for the reaction mechanism.