TY - JOUR
T1 - Samarium Diiodide Acting on Acetone—Modeling Single Electron Transfer Energetics in Solution
AU - Steiner, Luca
AU - Achazi, Andreas J.
AU - Vlaisavljevich, Bess
AU - Miro, Pere
AU - Paulus, Beate
AU - Kelterer, Anne Marie
N1 - Publisher Copyright:
© 2022 by the authors.
PY - 2022/12
Y1 - 2022/12
N2 - 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.
AB - 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.
KW - computational chemistry
KW - density functional theory
KW - effective core potential
KW - HMPA influence
KW - ketyl radical
KW - lanthanoide chemistry
KW - reduction potential
UR - http://www.scopus.com/inward/record.url?scp=85144497571&partnerID=8YFLogxK
U2 - 10.3390/molecules27248673
DO - 10.3390/molecules27248673
M3 - Article
C2 - 36557814
AN - SCOPUS:85144497571
SN - 1420-3049
VL - 27
JO - Molecules
JF - Molecules
IS - 24
M1 - 8673
ER -