Synthesis, crystal structure, spectral characterization, and theoretical study of glycolato peroxido complexes of vanadium(V)

• Published in: Structural chemistry 2016-04, Vol.27 (2), p.605-615
• Main Authors: Orešková, Gabriela, Chrappová, Jana, Puškelová, Jarmila, Šimunek, Ján, Schwendt, Peter, Noga, Jozef, Gyepes, Róbert
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Computer Applications in Chemistry; Original Research; Physical Chemistry; Theoretical and Computational Chemistry
• ISSN: 1040-0400; 1572-9001
• DOI: 10.1007/s11224-015-0593-9

We present the crystal structures and spectral characterization of two glycolato peroxido complexes of vanadium(V) with divalent cations. Assignment of their experimental infrared and Raman solid-state spectra was corroborated by gas-phase and periodic density functional calculations. First, the conventional BP86, PBE, and B3LYP exchange–correlation functionals were applied; their long-range-corrected variants LC-BP86 and CAM-B3LYP were subsequently utilized to evaluate their applicability in reproducing the solid-state structures and spectroscopic properties of the [V 2 O 2 (O 2 ) 2 (C 2 H 2 O 3 ) 2 ] 2− anion. Band assignments are presented in terms of potential energy distribution contributions. The structure of [Zn(H 2 O) 6 ][V 2 O 2 (O 2 ) 2 (C 2 H 2 O 3 ) 2 ]·2H 2 O obtained in solid state using the PBE functional is in very good agreement with the X-ray single-crystal structure. Computed vibrational frequencies and infrared intensities provided a satisfactory fit for the observed spectrum. 51 V NMR chemical shifts were calculated using optimized gas-phase geometries with the GIAO approach employing the B3PW91 functional, and they were correlated with experimentally observed shift measured for the aqueous solutions.