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

Autor: Steiner L; Institute of Physical und Theoretical Chemistry, NAWI Graz, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria.; Institut für Chemie und Biochemie, Freie Universität Berlin, Arnimallee 22, 14195 Berlin, Germany., Achazi AJ; Physikalisch-Chemisches Institut, Justus-Liebig-Universität Giessen, 35392 Giessen, Germany., Vlaisavljevich B; Department of Chemistry, University of South Dakota, 414 E. Clark St., Vermillion, SD 57069, USA., Miro P; Department of Chemistry, University of South Dakota, 414 E. Clark St., Vermillion, SD 57069, USA., Paulus B; Institut für Chemie und Biochemie, Freie Universität Berlin, Arnimallee 22, 14195 Berlin, Germany., Kelterer AM; Institute of Physical und Theoretical Chemistry, NAWI Graz, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria.
Jazyk: angličtina
Zdroj: Molecules (Basel, Switzerland) [Molecules] 2022 Dec 08; Vol. 27 (24). Date of Electronic Publication: 2022 Dec 08.
DOI: 10.3390/molecules27248673
Abstrakt: 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.
Databáze: MEDLINE
Externí odkaz:
Nepřihlášeným uživatelům se plný text nezobrazuje