title: Formic acid interaction with the uranyl(VI) ion: structural and photochemical characterization.
abstract: Complex formation between the uranyl(VI) ion and formic acid was studied by infrared absorption (IR) and X-ray absorption (EXAFS) spectroscopy as well as density functional theory (DFT) calculations. In contrast to the acetate ion which forms exclusively a bidentate complex with uranyl(VI), the formate ion binds to uranyl(VI) in a unidentate fashion. The photochemistry of the uranyl(VI)-formic acid system was explored by DFT calculations and photoreduction of uranyl(VI) in the presence of formic acid was found to occur via an intermolecular process, that is, hydrogen abstraction from hydrogenformate by the photo-excited uranyl(VI). There is no photo-induced decarboxylation of uranyl(VI) formate via an intramolecular process, presumably due to lack of a C=C double bond.
authors.affiliation: Institute of Resource Ecology, Helmholtz-Zentrum Dresden-Rossendorf, Bautzner Landstraße 400, 01328 Dresden, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Lucks
authors.forename: André
authors.initials: A
authors.lastname: Rossberg
authors.forename: Satoru
authors.initials: S
authors.lastname: Tsushima
authors.forename: Harald
authors.initials: H
authors.lastname: Foerstendorf
authors.forename: Karim
authors.initials: K
authors.lastname: Fahmy
authors.forename: Gert
authors.initials: G
authors.lastname: Bernhard
mesh_terms: D005561:Formates / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D055668:Photochemical Processes; D011789:Quantum Theory; D014501:Uranium / Q000737:chemistry*
chemical_list: D005561:Formates; D007477:Ions; D009942:Organometallic Compounds; C030544:formic acid; D014501:Uranium