Synthesis, crystal structure, spectral characterization, and theoretical study of glycolato peroxido complexes of vanadium(V)
Abstrakt
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 [V2O2(O-2)(2)(C2H2O3)(2)](2-) anion. Band assignments are presented in terms of potential energy distribution contributions.
The structure of [Zn(H2O)(6)][V2O2(O-2)(2)(C2H2O3)(2)] . 2H2O 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.
V-51 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.