Sm(II), computational study, reactivity
Sm(II) diiodide is widely used in organic synthesis as a reducing agent. It can reduce water forming hydrogen gas and has also been used in reduction reactions of functional groups such as esters, anhydrides, amides, carbonyls, and arenes. However, the mechanism of these reactions is not completely understood, making it difficult to improve experimental design. It is known that the solvent has a significant effect on the reactivity and that the reaction proceeds either through electron transfer or proton coupled electron transfer mechanisms. We perform density functional theory (DFT) calculations to first study the speciation of [Sm(II)(THF)n(H2O)m]2+, Sm(II)I2(THF)n(H2O)m, [Sm(II)I(THF)n(H2O)m]+, and [Sm(III)(THF)n(H2O)m]3+ in water, THF, and mixtures. By determining the energy profile of these species, we aim to determine which species are present under experimentally relevant conditions. Future work will explore the energetically accessible pathways of Sm(II) reduction reactions.
Fasihianifard, Parisa, "Computational Study of Sm(II) Reactivity in Water, THF, and Mixtures" (2021). IdeaFest. 297.