[Rh^II(ttp)]₂ | 663189-71-7

• 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^II(ttp)]₂
• 英文别名: [Rh^II(5,10,15,20-tetra-p-tolylporphyrine)]₂；Rh(5,10,15,20-tetratolylporphyrin)；[rhodium(II)(5,10,15,20-tetratolylporphyrin)]；Rh(II)(5,10,15,20-tetratolylporphyrinato)；Rh(ttp)
• CAS: 663189-71-7
• 化学式: C₄₈H₃₆N₄Rh
• 分子量: 771.746
• InChiKey: PRUNHMFWAJOCGW-NHZJRHMYSA-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：

  二甲基环已酮 、 [Rh^II(ttp)]₂ 以 neat (no solvent) 为溶剂， 以40%的产率得到[Rh(5,10,15,20-tetratolylporphyrinato)(COCHMe(CH2)3COMe)]
  参考文献：
  名称：

  铑（III）卟啉对酮的轻度和选择性C（CO）-C（α）键裂解：范围和机理

  摘要：

  发现铑（III）卟啉在低至50°C的温度下会受到水促进的酮的选择性C（CO）–C（α）键活化（CCA）。酮的酰基转移到铑中心，并且烷基片段相应地氧化成羰基部分。水的羟基通过动力学α-碳-氢键活化（α-CHA）产物的水解转移到卟啉铑上，得到Rh III（ttp）OH（ttp = 5,10,15,20-四甲苯基卟啉二价阴离子） ），然后裂解酮的C（CO）–C（α）键。

  DOI：

  10.1021/om200788p
• 作为产物：
  描述：

  Rh(ttp)Me 以 甲醇 为溶剂， 生成 甲基自由基 、 [Rh^II(ttp)]₂
  参考文献：
  名称：

  甲基(卟啉)铑(III)配合物中Rh-C键解离能的测定：光声量热法的新应用

  摘要：

  在室温下在甲醇中研究了 RhCH3(ttp) 和 RhCH3(tmp)（ttp = 5,10,15,20-四甲苯基卟啉，tmp = 5,10,15,20-四甲基卟啉）的光解：光解的量子产率分别确定为 0.51 和 0.54，并且通过光声量热法测量的 Rh-C 键解离能（分别为 227 和 219 kJ mol-1）大于 Co-C 键的解离能。

  DOI：

  10.1246/cl.2001.284
• 作为试剂：
  描述：

  rhodium(III) tetrakis(4-tolyl)porphyrin chloride 、 环辛烷 在 [Rh^II(ttp)]₂ K₂CO₃ 作用下， 以 further solvent(s) 为溶剂， 以33%的产率得到Rh(5,10,15,20-tetratolylporphyrinato)(n-octyl)
  参考文献：
  名称：

  Metalloradical-Catalyzed Aliphatic Carbon−Carbon Activation of Cyclooctane

  摘要：

  The aliphatic carbon-carbon activation of c-octane was achieved via the addition of Rh(ttp)H to give Rh(ttp)(n-octyl) in good yield under mild reaction conditions. The aliphatic carbon-carbon activation was Rh-II(ttp)-catalyzed and was very sensitive to porphyrin sterics.

  DOI：

  10.1021/ja101586w

文献信息

• Carbon–nitrogen bond activation of amines by rhodium(III) porphyrin complexes
  作者：Ching Chi Au、Tsz Ho Lai、Kin Shing Chan

  DOI：10.1016/j.jorganchem.2010.02.007

  日期：2010.5

  Carbon–nitrogen bond activation of amines by rhodium porphyrin chloride has been achieved to give rhodium porphyrin alkyl complexes. Rhodium porphyrin hydride and rhodium porphyrin dimer were proposed as the intermediates in cleaving the C–N bond.

  已经实现了氯化卟啉铑对胺的碳-氮键活化，从而得到铑卟啉烷基络合物。提出了氢化卟啉铑和卟啉铑二聚体作为裂解C-N键的中间体。
• Metalloradical-Catalyzed Selective 1,2-Rh-H Insertion into the Aliphatic Carbon–Carbon Bond of Cyclooctane
  作者：Yun Wai Chan、Bas de Bruin、Kin Shing Chan

  DOI：10.1021/acs.organomet.5b00183

  日期：2015.6.22

  The selective aliphatic carboncarbon activation of cyclo-octane (c-octane) was achieved via the Rh-II(ttp)-catalyzed 1,2-addition of Rh(ttp)H to give Rh(ttp)(n-octyl) (ttp = tetratolylporphyrinato dianion) in good yield under mild reaction conditions. This mechanism is further supported by DFT calculations. The reaction worked only with the sterically accessible Rh(ttp) porphyrin complex but not with the bulky Rh(tmp) system (tmp = tetrakismesitylporphyrinato dianion), thus showing the highly steric sensitivity of carboncarbon bond activation by transition metal complexes.
• Base-Promoted Vinyl Carbon–Bromine Bond Cleavage by Group 9 Metalloporphyrin Complexes
  作者：Ka Lai Wong、Chen Chen、Kin Shing Chan

  DOI：10.1021/acs.organomet.6b00228

  日期：2016.6.13

  Base-promoted vinyl carbon-bromine bond cleavage of styryl bromide by group 9 metalloporphyrin complexes was achieved to give the metal(III) porphyrin styryls M(ttp)(styryl) (ttp = 5,10,15,20-tetra:p-tolylporphyrinato dianion). Mechanistic studies suggest that [M-II(ttp)](2) (M = Rh, Ir) cleaves the vinyl C-Br bond via an addition-elimination mechanism. The much less reactive Co-II(ttp) undergoes a radical recombination with styryl radical which is generated by the hydroxide reduction of styryl bromide to give a radical anion with subsequent C-Br cleavage.
• Sterically Enhanced, Selective C(CO)−C(α) Bond Cleavage of a Ketones by Rhodium Porphyrin Methyl
  作者：Hong Sang Fung、Bao Zhu Li、Kin Shing Chan

  DOI：10.1021/om1007852

  日期：2010.10.25

  Selective carbon(CO) carbon(a) bond activation of ketones was achieved by rhodium(III) 5,10, 15,20-tetrakis-4-toylporphyrinato methyl (Rh(ttp)Me (1)) to yield the corresponding rhodium porphyrin acyls at temperatures as low as 50 degrees C. More hindered isopropyl ketones were much more reactive than ethyl or methyl ketones. Rh(ttp)OH(3a)was proposed to be the intermediate to cleave the C(CO)-C(alpha) bond.