Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/10379
Title: Oxoperoxo Vanadium(V) Complexes of l-Lactic Acid: Density Functional Theory Study of Structure and NMR Chemical Shifts
Authors: Justino, Licínia L. G. 
Ramos, M. Luísa 
Nogueira, Fernando 
Sobral, Abilio J. F. N. 
Geraldes, Carlos F. G. C. 
Kaupp, Martin 
Burrows, Hugh D. 
Fiolhais, Carlos 
Gil, Victor M. S. 
Issue Date: 18-Aug-2008
Publisher: American Chemical Society
Issue Date: 18-Aug-2008
Publisher: American Chemical Society
Citation: Inorganic Chemistry. 47:16 (2008) 7317-7326
Abstract: Various combinations of density functionals and pseudopotentials with associated valence basis-sets are compared for reproducing the known solid-state structure of [V2O2(OO)2l-lact2]2−cis. Gas-phase optimizations at the B3LYP/SBKJC level have been found to provide a structure that is close to that seen in the solid state by X-ray diffraction. Although this may result in part from error compensation, this optimized structure allowed satisfactory reproduction of solution multinuclear NMR chemical shifts of the complex in all-electron DFT-IGLO calculations (UDFT-IGLO-PW91 level), suggesting that it is probably close to that found in solution. This combination of approaches has subsequently been used to optimize the structures of the vanadium oxoperoxo complexes [V2O3(OO)l-lact2]2−cis, [V2O3(OO)l-lact2]2−trans, and [VO(OO)(l-lact)(H2O)]−cis. The 1H, 13C, 51V, and 17O NMR chemical shifts for these complexes have been calculated and compared with the experimental solution chemical shifts. Excellent agreement is seen with the 13C chemical shifts, while somewhat inferior agreement is found for 1H shifts. The 51V and 17O chemical shifts of the dioxo vanadium centers are well reproduced, with differences between theoretical and experimental shifts ranging from 22.9 to 35.6 ppm and from 25.1 to 43.7 ppm, respectively. Inferior agreement is found for oxoperoxo vanadium centers, with differences varying from 137.3 to 175.0 ppm for 51V shifts and from 148.7 to 167.0 ppm for 17O(oxo) shifts. The larger errors are likely to be due to overestimated peroxo O−O distances. The chosen methodology is able to predict and analyze a number of interesting structural features for vanadium(V) oxoperoxocomplexes of α-hydroxycarboxylic acids.
URI: http://hdl.handle.net/10316/10379
ISSN: 0020-1669
DOI: 10.1021/ic800405x
Rights: openAccess
Appears in Collections:FCTUC Ciências da Vida - Artigos em Revistas Internacionais
FCTUC Física - Artigos em Revistas Internacionais
FCTUC Química - Artigos em Revistas Internacionais

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