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Using Laser Scanning Microscopy to Determine Electromigration in Molybdenum Disilicide

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Quantifying the electrostatic driving force behind SmI2 reductions.

Hani Farran¹, Shmaryahu Hoz

¹Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900 Israel.

Organic Letters

|October 16, 2008

Summary

Electron transfer reactions between samarium(II) iodide (SmI2) and benzophenone derivatives are exothermic, contrary to predictions. Electrostatic attraction between the radical anion and Sm(3+) drives this observed exothermicity.

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Spatial Separation of Molecular Conformers and Clusters

Spatial Separation of Molecular Conformers and Clusters

Published on: January 9, 2014

Area of Science:

Physical Chemistry
Organic Chemistry
Electrochemistry

Background:

Electron transfer reactions are fundamental in chemistry.
Samarium(II) iodide (SmI2) is a powerful reducing agent.
Benzophenone derivatives are commonly used in photochemistry and electron transfer studies.

Purpose of the Study:

To determine the equilibrium constant for electron transfer between SmI2 and substituted benzophenones.
To investigate the thermodynamic driving forces of these electron transfer reactions.
To reconcile discrepancies between theoretical redox potential predictions and experimental observations.

Main Methods:

Determination of equilibrium constants for electron transfer reactions.
Calculation of Gibbs free energy (DeltaG(eq)) for the reactions.
Analysis of redox potentials to predict thermodynamic favorability.

Main Results:

Electron transfer reactions were found to be exothermic, with DeltaG(eq) values ranging from -5.1 to -1.6 kcal/mol.
Redox potential calculations predicted endothermic reactions (approx. 25 kcal/mol).
A significant deviation between predicted and observed thermodynamics was observed.

Conclusions:

The experimental exothermicity contradicts predictions based solely on redox potentials.
Electrostatic attraction between the generated radical anion and Sm(3+) ions is proposed as the driving force for exothermicity.
This electrostatic interaction significantly stabilizes the products, altering the reaction's overall thermodynamics.