title: The role of H2O in the electron transfer-activation of substrates using SmI2: insights from DFT.
abstract: The first detailed theoretical study on the synthetically important electron transfer (ET) reductant SmI2-H2O has been conducted in the context of the activation of important alkyliodide, ketone, lactone and ester substrates, processes of importance in cross-coupling. Our studies give major insights into the nature of the reagent and suggest that; (i) H2O has a high affinity for Sm(ii) and displaces iodine from the metal center; (ii) SmI2-H2O has 6-7 molecules of H2O directly bound to the metal center; (iii) binding of H2O to Sm(II) promotes coordination of the substrate to Sm(II) and subsequent ET; (iv) resultant ketyl radicals are stabilized by hydrogen-bonding to H2O. The findings add greatly to the understanding of SmI2-H2O and the role of H2O in ET processes, and will facilitate the design of new processes initiated by reductive ET.
authors: Laboratoire de Physique et Chimie des Nano-Objets, INSA, Université Paul Sabatier, 135 Avenue de Rangueil, 31077 Toulouse Cedex 4, France. laurent.maron@irsamc.ups-tlse.fr.
authors: Xuefei
authors: X
authors: Zhao
authors: Université Lyon 1, CNRS UMR 5246, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, 43 Boulevard du 11 Novembre 1918, F-69622, Villeurbanne, France.
authors: Lionel
authors: L
authors: Perrin
authors: School of Chemistry, University of Manchester, Manchester, M13 9PL, UK.
authors: David J
authors: DJ
authors: Procter
authors: Laboratoire de Physique et Chimie des Nano-Objets, INSA, Université Paul Sabatier, 135 Avenue de Rangueil, 31077 Toulouse Cedex 4, France. laurent.maron@irsamc.ups-tlse.fr.
authors: Laurent
authors: L
authors: Maron