title: Dinuclear fluoro-peroxovanadium(v) complexes with symmetric and asymmetric peroxo bridges: syntheses, structures and DFT studies.
abstract: Two new dinuclear fluoro peroxovanadium(v) complexes, Cs3[V2O2(O2)4F] x H2O (1) and Cs3[V2O2(O2)3F3] x 2HF x H2O (2), were prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and X-ray crystallography. While the anion in possesses an asymmetric structure with a micro-eta1:eta2 bridging peroxo group, the [V2O2(O2)3F3]3- ion in exhibits a symmetrical structure with a unique mu-fluoro and micro-eta2:eta2 peroxo double bridge. The X-ray structure data were compared with equilibrium and vibrationally-averaged (effective) DFT calculated geometries. The decomposition reactions of and in aqueous solution were studied by 51V NMR spectroscopy. The calculations of vibrationally averaged NMR chemical shifts (DFT-GIAO) were used to support the empirical assignment of NMR signals and afforded excellent agreement with experimental values for the studied peroxovanadium species. The ESI mass spectra of the prepared compounds are in accordance with the assignment of NMR spectra and with DFT study.
authors.affiliation: Comenius University, Faculty of Natural Sciences, Department of Inorganic Chemistry, Mlynská dolina, Bratislava, Slovak Republic.
authors.forename: Jana
authors.initials: J
authors.lastname: Chrappová
authors.forename: Peter
authors.initials: P
authors.lastname: Schwendt
authors.forename: Michal
authors.initials: M
authors.lastname: Sivák
authors.forename: Michal
authors.initials: M
authors.lastname: Repiský
authors.forename: Vladimir G
authors.initials: VG
authors.lastname: Malkin
authors.forename: Jaromír
authors.initials: J
authors.lastname: Marek
mesh_terms: D000838:Anions; D018360:Crystallography, X-Ray / Q000379:methods; D005461:Fluorine / Q000737:chemistry*; D007477:Ions; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D015233:Models, Statistical; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D012984:Software; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D013055:Spectrophotometry, Infrared / Q000379:methods; D013696:Temperature; D014639:Vanadium / Q000737:chemistry*
chemical_list: D000838:Anions; D007477:Ions; D009942:Organometallic Compounds; D014639:Vanadium; D005461:Fluorine; D010100:Oxygen