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Redox Reactions01:24

Redox Reactions

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Oxidation-reduction or redox reactions involve the transfer of electrons from one molecule or atom to another. When an atom gains an electron, another atom must lose an electron, meaning oxidation and reduction must occur together. Since the redox occurs in pairs, the atom that gets oxidized is also called the reducing agent or reductant, and the atom that is reduced is also called the oxidizing agent or oxidant. A straightforward way to remember the definitions of oxidation and reduction is...
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Redox Reactions01:27

Redox Reactions

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Redox reactions are vital biochemical processes that underpin energy metabolism in cells. These reactions involve the transfer of electrons between molecules, occurring in tandem as oxidation and reduction. Oxidation refers to the loss of electrons, while reduction denotes their gain. This coupling ensures the seamless flow of electrons through metabolic pathways. For example, in bacterial metabolism, glucose undergoes oxidation to carbon dioxide, while oxygen is simultaneously reduced to...
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Redox Titration: Other Oxidizing and Reducing Agents01:26

Redox Titration: Other Oxidizing and Reducing Agents

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Besides iodine, other oxidizing or reducing agents can serve as titrants in redox titrations. Common oxidizing titrants include KMnO4, cerium(IV), and K2Cr2O7. The choice of oxidizing titrants depends on factors like stability, cost, analyte strength, and reaction rate between the analyte and titrant. KMnO4 is a strong oxidizing titrant that reduces from Mn(VII) to Mn(II) in a highly acidic solution, simultaneously oxidizing the analyte to a higher oxidation state. In this case, KMnO4 acts as a...
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Ladder Diagrams: Redox Equilibria01:30

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Ladder diagrams are useful tools for understanding redox equilibrium reactions, especially the effects of concentration changes on the electrochemical potential of the reaction. The vertical axis in the redox ladder diagrams represents the electrochemical potential, E. The area of predominance is demarcated using the Nernst equation.
Consider the Fe3+/Fe2+ half-reaction, which has a standard-state potential of +0.771 V. At potentials more positive than +0.771 V, Fe3+ predominates, whereas Fe2+...
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In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
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Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate02:21

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Alkenes can be dihydroxylated using potassium permanganate.  The method encompasses the reaction of an alkene with a cold, dilute solution of potassium permanganate under basic conditions to form a cis-diol along with a brown precipitate of manganese dioxide.
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Manipulación de la nucleofilia terminal del hidróxido de hierro a través del redox

Jeewhan Oh1, Kurtis M Carsch1, Shao-Liang Zheng1

  • 1Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States.

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|January 16, 2026
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Resumen

El estado de oxidación del hierro altera drásticamente la reactividad de los complejos hidroxo de hierro. El hierro ferroso actúa como un nucleófilo, vinculando reversiblemente el CO2, mientras que el hierro férrico actúa como un electrófilo, reaccionando con los carborrádicos.

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Área de la Ciencia:

  • Química inorgánica
  • Química organometálica
  • Química bioorgánica

Sus antecedentes:

  • Los complejos hidroxo ferrosos terminales de alto espín son intermedios clave en varios ciclos catalíticos.
  • La comprensión de los factores electrónicos y estéricos que rigen su reactividad es crucial para el diseño del catalizador.

Objetivo del estudio:

  • Investigar la influencia del estado de oxidación del hierro en la reactividad de un complejo hidroxo terminal.
  • Explorar las propiedades nucleófilas y electrófilas de los complejos hidroxoferrosos y férricos.
  • Para aclarar el papel del medio ligando en la modulación de la hidroxoactividad del hierro.

Principales métodos:

  • Síntesis y caracterización de complejos hidroxo ferrosos y férricos terminales de alto espín dentro de un andamio de ligando de dipirrina.
  • Estudios de reactividad con varios electrófilos (CO2, CS2, nitriles, isocianatos) y carboradicales.
  • Caracterización espectroscópica que incluye cristalografía de rayos X de un solo cristal, espectroscopia Mössbauer 57Fe y espectroscopia IR.

Principales resultados:

  • El complejo ferroso (EmL) Fe ((OH) exhibe reactividad nucleofílica, capturando de manera reversible el CO2 para formar un adducto de bicarbonato.
  • El análogo férrico (EmL) Fe ((OH) muestra reactividad electrofílica, experimentando recombinación radical con carboradicales.
  • La variación sistemática de los ligandos terminales (X) en los análogos ferrosos revela tendencias en el carácter nucleofílico.

Conclusiones:

  • El estado de oxidación del hierro dicta el carácter nucleófilo/electrófilo de la fracción Fe-OH terminal.
  • La electronegatividad y la basicidad de los ligandos influyen significativamente en la reactividad observada.
  • Estos hallazgos proporcionan información sobre los mecanismos de la hidroxilación mediada por el hierro y la captura de CO2.