[Rh(meso-tetramesitylporphyrinato)(Si(t)BuMe2)] | 823835-03-6

• 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(meso-tetramesitylporphyrinato)(Si(t)BuMe2)]
• 英文别名: Rh(tmp)Si(t)BuMe2；Rh(tetramesitylporphyrinato)(Si(t)BuMe2)
• CAS: 823835-03-6
• 化学式: C₆₂H₆₇N₄RhSi
• 分子量: 999.232
• InChiKey: PBDAXMIAHXSWBM-WSJWEZPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  (tetramesitylporphyrinato)rhodium(II) 、 叔丁基氰基二甲基硅烷 在 三苯基膦 作用下， 以 not given 为溶剂， 以2%的产率得到[Rh(meso-tetramesitylporphyrinato)(Si(t)BuMe2)]
  参考文献：
  名称：

  Mechanistic Studies of Si−CN and C−NC Bond Activation of Silylnitriles and Alkyl Isonitriles by Rhodium Porphyrin Radical:  Novel Cyanide Transfer

  摘要：

  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.

  DOI：

  10.1021/om0605276

文献信息

• Oxidative Addition of Silyl Cyanides to Rhodium Porphyrin Radical:  Isocyanide or Cyanide Transfer Mechanism
  作者：Kin Shing Chan、Lirong Zhang、Chun Wah Fung

  DOI：10.1021/om049253h

  日期：2004.12.1

  Rhodium porphyrin radical, coordinated with pyridine, activated the carbon−silicon bond of silyl cyanides to yield rhodium porphyrin silyls and cyanide. The reaction with Me3SiCN exhibited second-order kinetics, rate = kobsd[Rh(tmp)][Me3SiCN], at a sufficiently high concentration of pyridine, and the mechanism was interpreted to involve a cyanide or isocyanide group transfer to rhodium radical.

  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。