Rh(octaethylporphyrinato)(PF6) | 108638-60-4

• 英文名称: Rh(octaethylporphyrinato)(PF6)
• CAS: 108638-60-4
• 化学式: C₃₆H₄₄N₄Rh*F₆P
• 分子量: 780.642
• InChiKey: VBUXQQZZAPUYJQ-YAJYDHHFSA-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：

  吡啶 、 Rh(octaethylporphyrinato)(PF6) 以 二氯甲烷 、 甲苯 为溶剂， 生成 Rh(octaethylporphyrinato)(pyridine)(1+)
  参考文献：
  名称：

  Synthesis and Reactivity of Porphyrinatorhodium(II)−Triethylphosphine Adducts:  The Role of PEt₃ in Stabilizing a Formal Rh(II) State

  摘要：

  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.

  DOI：

  10.1021/ja001364u

文献信息

• Aromatic and Benzylic C−H Bond Activation in the System Bis(dicarbonylrhodium(I))- porphyrinate−Hydrocarbon Solvent
  作者：James P. Collman、Roman Boulatov

  DOI：10.1021/ic0011112

  日期：2001.5.1

  Metalation of C6H6 has been known for a long time as a side reaction occurring in refluxing benzene solutions of Rh-2(CO)(4)(TPP) (TTP = tetraphenylporphyrin). Rather than representing the intrinsic reactivity of this complex, such hydrocarbon activation proceeds via Rh-II(por) and Rh-III(por) derivatives resulting from oxidation of Rh-2(CO)(4)(TPP) with adventitious H2O and/or O-2. This reaction can be extended to other aromatic substrates and represents an efficient synthetic route to certain organometallic Rh-III(TPP) derivatives.[GRAPHICS]