Aggregation state and reducing power of the samarium diiodide–DMPU complex in acetonitrile

A Samarium “Soluble” Anode: A New Source of SmI2 Reagent for Electrosynthetic Application

“…To the best of our knowledge, although the electrochemical characteristics of SmI 2 have been widely studied, among others by Flowers et al.,10–13 the electrochemical synthesis of SmI 2 by oxidation has never been described and only very few electrochemical studies have been dedicated to electrogenerated samarium derivatives. Indeed, only two approaches have been described to generate divalent samarium by electrochemical reduction for synthetic applications.…”

Recent advances in the chemoselective reduction of functional groups mediated by samarium(ii) iodide: a single electron transfer approach

“…entries 5 and 6). [7][8][9][10][11][12][13][14][15] The redox potential of SmI 2 and chemoselectivity of the reduction can also be influenced by solvent used for the preparation of the reagent (e.g. entries 1 and 3 vs. 9 and 10).…”

Activation of CO2 by Vanadium Nitrogenase

“…[100,102,103] The reduction potential of Sm II I 2 in THF has been determined to be À0.89 Vv s. SCE; [106] however,t he dielectric constant and dipole moment of DMF is similart ot he ligand 1,3-dimethyltetrahydropyrimidin-2(1H)-one (DMPU) and is therefore expected to render the solution reduction potential closertoa pproximately À1.5 Vv s. SCE. [105,107,108] Using these improved reduction conditions, the Fischer-Tropsch-like hydrogenation of CO 2 with V-cluster can be accomplished. When CO 2 reduction withV -cluster is performed in the organic solventd imethylformamide and driven by SmI 2 , CO and gaseous hydrocarbonsc an be produced.…”

“…Based on the observed formation of a distinct Sm II I 2 species in the nitrogenase cofactor experiments, a DMF‐coordinated Sm II I 2 complex is believed to be formed in situ . The reduction potential of Sm II I 2 in THF has been determined to be −0.89 V vs. SCE; however, the dielectric constant and dipole moment of DMF is similar to the ligand 1,3‐dimethyltetrahydropyrimidin‐2(1 H )‐one (DMPU) and is therefore expected to render the solution reduction potential closer to approximately −1.5 V vs. SCE …”