tetraphenylporphyrinhydridorhodium(III) | 103533-54-6

• 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: tetraphenylporphyrinhydridorhodium(III)
• 英文别名: rhodium(III) porphyrin hydride
• CAS: 103533-54-6
• 化学式: C₄₄H₂₉N₄Rh
• 分子量: 716.647
• InChiKey: JGBKZHLGHDFVFS-YKKPBKTHSA-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

• 作为反应物：
  描述：

  tetraphenylporphyrinhydridorhodium(III) 以 氘代苯 为溶剂， 生成 {(tetraphenylporphinato)Rh}2
  参考文献：
  名称：

  Wayland, Bradford B.; Van Voorhees, Seth L.; Wilker, Charles, Inorganic Chemistry, 1986, vol. 25, # 22, p. 4039 - 4042

  摘要：

  DOI：
• 作为产物：
  描述：

  iodo(5,10,15,20-tetraphenylporphyrinato-κ4N)rhodium(III) 、 sodium tetrahydroborate 在 sodium hydroxide 、 溶剂黄146 作用下， 以 乙醇 、 水 为溶剂， 以62%的产率得到tetraphenylporphyrinhydridorhodium(III)
  参考文献：
  名称：

  Wayland, Bradford B.; Van Voorhees, Seth L.; Wilker, Charles, Inorganic Chemistry, 1986, vol. 25, # 22, p. 4039 - 4042

  摘要：

  DOI：

文献信息

• Production of Formamides from CO and Amines Induced by Porphyrin Rhodium(II) Metalloradical
  作者：Jiajing Zhang、Wentao Zhang、Minghui Xu、Yang Zhang、Xuefeng Fu、Huayi Fang

  DOI：10.1021/jacs.8b03029

  日期：2018.5.30

  on the activation of C≡O bond by π-back bonding from the transition metal center were developed during the past decades. Herein, a new CO activation method, in which the CO was converted to the active acyl-like metalloradical, [(por)Rh(CO)]• (por = porphyrin), was reported. The reactivity of [(por)Rh(CO)]• and other rhodium porphyrin compounds, such as (por)RhCHO and (por)RhC(O)NH nPr, and corresponding

  将一氧化碳 (CO) 转化为石化原料和精细化学品至关重要。在过去的几十年中，开发了许多基于通过过渡金属中心的 π 背键激活 C≡O 键的策略。在此，报道了一种新的 CO 活化方法，其中将 CO 转化为活性酰基类金属基团 [(por)Rh(CO)]• (por = 卟啉)。[(por)Rh(CO)]• 和其他铑卟啉化合物，如 (por)RhCHO 和 (por)RhC(O)NH nPr 的反应性以及相应的机制研究是通过实验和计算进行的，并启发了设计一种具有 100% 原子经济性的新转化系统，可使用卟啉铑 (II) 金属基促进胺羰基化为甲酰胺。遵循这种基于自由基的途径，
• Synthesis and Reactivity of Porphyrinatorhodium(II)−Triethylphosphine Adducts:  The Role of PEt₃ in Stabilizing a Formal Rh(II) State
  作者：James P. Collman、Roman Boulatov

  DOI：10.1021/ja001364u

  日期：2000.12.1

  Rh(por)H, where por is an octaethyl- or meso-tetraphenylporphyrin dianion,reacts with triethylphosphine to form stable mononuclear paramagnetic formally-Rh-II complexes, Rh(OEP)(PEt3) and Rh(TPP)-(PEt3)(2). The former adduct is also obtained as the sole product of the reaction between Rh-2(OEP)(2) and FEt3. The EPR spectroscopy at 77 K shows both complexes to have mainly porphyrin-based HOMOs. The composition and the reactivity of Rh(TPP.-)(PEt3)(2) support its formulation as Rh-III(TPP'-)(PEt3)(2). In contrast, Rh(OEP)(PEt3)(2) demonstrates the reactivity of both a Rh-II d(7) center and a porphyrin pi -anion radical. The adduct reacts with O-2 as a Rh-II(por) species, originally forming a Rh-III-superoxido derivative. In contrast, with water Rh(OEP)(PEt3) reacts as a porphyrin sz-anion radical, yielding a Rh-III-octaethylphlorin complex. The latter is the first characterized phlorin complex of a heavy transition metal. The dual reactivity of Rh(OEP)(PEt3) is proposed to arise from thermal excitation of the unpaired electron from the porphyrin-based HOMO onto the metal-based LUMO (d sigma*(Rh-P)) Unlike the other reported 1:1 adducts of Rh-II(por) species with sigma -basic ligands, Rh(OEP)(PEt3) is remarkably stable toward disproportionation to Rh-I and Rh-III. To understand the origin of this stability, the affinity of Rh-III(OEP)(+) toward PEt3 and pyridine was measured spectrophotometrically. The high binding affinity of PEt3 to Rh(OEP) is proposed as the underlying cause of the increased stability of Rh(OEP)(PEt3) toward disproportionation.
• Anti-Markovnikov Hydrofunctionalization of Olefins Mediated by Rhodium–Porphyrin Complexes
  作者：Melanie S. Sanford、John T. Groves

  DOI：10.1002/anie.200351941

  日期：2004.1.23