Samarium Diiodide Acting on Acetone—Modeling Single Electron Transfer Energetics in Solution

Luca Steiner, Andreas J. Achazi, Bess Vlaisavljevich, Pere Miro, Beate Paulus, Anne Marie Kelterer*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Samarium diiodide is a versatile single electron transfer (SET) agent with various applications in organic chemistry. Lewis structures regularly insinuate the existence of a ketyl radical when samarium diiodide binds a carbonyl group. The study presented here investigates this electron transfer by the means of computational chemistry. All electron CASPT2 calculations with the inclusion of scalar relativistic effects predict an endotherm electron transfer from samarium diiodide to acetone. Energies calculated with the PBE0-D3(BJ) functional and a small core pseudopotential are in good agreement with CASPT2. The calculations confirm the experimentally measured increase of the samarium diiodide reduction potential through the addition of hexamethylphosphoramide also known as HMPA.

Original languageEnglish
Article number8673
Issue number24
Publication statusPublished - Dec 2022


  • computational chemistry
  • density functional theory
  • effective core potential
  • HMPA influence
  • ketyl radical
  • lanthanoide chemistry
  • reduction potential

ASJC Scopus subject areas

  • Analytical Chemistry
  • Chemistry (miscellaneous)
  • Molecular Medicine
  • Pharmaceutical Science
  • Drug Discovery
  • Physical and Theoretical Chemistry
  • Organic Chemistry


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