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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

908
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...
908
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

Ladder Diagrams: Redox Equilibria

768
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+...
768
Oxidation of Phenols to Quinones01:17

Oxidation of Phenols to Quinones

4.6K
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

Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate

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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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Related Experiment Video

Updated: Jan 18, 2026

Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase
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Manipulating Terminal Iron-Hydroxide Nucleophilicity through 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.

Journal of the American Chemical Society
|January 16, 2026
PubMed
Summary
This summary is machine-generated.

The oxidation state of iron dramatically alters the reactivity of iron hydroxo complexes. Ferrous iron acts as a nucleophile, reversibly binding CO2, while ferric iron acts as an electrophile, reacting with carboradicals.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Bioinorganic Chemistry

Background:

  • High-spin, terminal ferrous hydroxo complexes are key intermediates in various catalytic cycles.
  • Understanding the electronic and steric factors governing their reactivity is crucial for catalyst design.

Purpose of the Study:

  • To investigate the influence of iron oxidation state on the reactivity of a terminal hydroxo complex.
  • To explore the nucleophilic and electrophilic properties of ferrous and ferric iron hydroxo complexes.
  • To elucidate the role of ligand environment in modulating iron hydroxo reactivity.

Main Methods:

  • Synthesis and characterization of high-spin, terminal ferrous and ferric hydroxo complexes within a dipyrrin ligand scaffold.
  • Reactivity studies with various electrophiles (CO2, CS2, nitriles, isocyanates) and carboradicals.
  • Spectroscopic characterization including single-crystal X-ray crystallography, 57Fe Mössbauer spectroscopy, and IR spectroscopy.

Main Results:

  • The ferrous complex (EmL)Fe(OH) exhibits nucleophilic reactivity, reversibly capturing CO2 to form a bicarbonate adduct.
  • The ferric analogue (EmL)Fe(OH) displays electrophilic reactivity, undergoing radical recombination with carboradicals.
  • Systematic variation of terminal ligands (X) in ferrous analogues reveals trends in nucleophilic character.

Conclusions:

  • The oxidation state of iron dictates the nucleophilic/electrophilic character of the terminal Fe-OH moiety.
  • Ligand electronegativity and basicity significantly influence the observed reactivity.
  • These findings provide insights into the mechanisms of iron-mediated hydroxylation and CO2 capture.