Redox Reactivity of Organic Compounds

 

Redox Reactivity Profile of Organic Compounds

First electron-transfer potentials (V vs. reference). Blue = Reduction (LUMO), Red = Oxidation (HOMO). Hover for structures.

All Chemical Classes Hydrocarbons & Fullerenes Oxygen-containing Nitrogen-containing Halogenated Sulfur-containing Sort by: Potential (Negative to Positive) Sort by: Potential (Positive to Negative) Sort by: Chemical Class

Mechanistic Insights in Aprotic Solvents

In nonaqueous, aprotic solvents (like DMF or Acetonitrile), the first reduction step of an electrophilic organic molecule is typically a single-electron transfer to its Lowest Unoccupied Molecular Orbital (LUMO), generating a radical anion (M + e⁻ → M^•−). Conversely, nucleophilic molecules undergo oxidation by losing an electron from their Highest Occupied Molecular Orbital (HOMO), forming a radical cation (M − e⁻ → M^•+).

Because radical ions are highly reactive, extreme care must be taken regarding solvent purity. For example, trace water acts as a proton donor, which can immediately protonate a newly formed radical anion, shifting the mechanism from a reversible one-electron step to an irreversible multi-electron pathway.

Source Data: Izutsu, K. Electrochemistry in Nonaqueous Solutions, 2nd, Revised and Enlarged Edition; Wiley-VCH: Weinheim, 2010. Data adapted from Table 8.5 (Reductions, p. 256) and Table 8.7 (Oxidations, p. 269). Structures rendered via PubChem API.

Compound

Process

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