Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/10379
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dc.contributor.authorJustino, Licínia L. G.-
dc.contributor.authorRamos, M. Luísa-
dc.contributor.authorNogueira, Fernando-
dc.contributor.authorSobral, Abilio J. F. N.-
dc.contributor.authorGeraldes, Carlos F. G. C.-
dc.contributor.authorKaupp, Martin-
dc.contributor.authorBurrows, Hugh D.-
dc.contributor.authorFiolhais, C.-
dc.date.accessioned2009-06-26T10:34:40Z-
dc.date.available2009-06-26T10:34:40Z-
dc.date.issued2008-08-18-
dc.identifier.citationInorganic Chemistry. 47:16 (2008) 7317-7326en_US
dc.identifier.issn0020-1669-
dc.identifier.urihttp://hdl.handle.net/10316/10379-
dc.description.abstractVarious 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.en_US
dc.description.urihttp://dx.doi.org/10.1021/ic800405x-
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsopenAccesseng
dc.titleOxoperoxo Vanadium(V) Complexes of l-Lactic Acid: Density Functional Theory Study of Structure and NMR Chemical Shiftsen_US
dc.typearticleen_US
dc.identifier.doi10.1021/ic800405x-
uc.controloAutoridadeSim-
item.languageiso639-1en-
item.fulltextCom Texto completo-
item.grantfulltextopen-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.researchunitCFisUC – Center for Physics of the University of Coimbra-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.researchunitCFisUC – Center for Physics of the University of Coimbra-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.orcid0000-0002-8338-6441-
crisitem.author.orcid0000-0003-3125-3660-
crisitem.author.orcid0000-0001-6367-027X-
crisitem.author.orcid0000-0002-0837-8329-
crisitem.author.orcid0000-0003-3127-2298-
crisitem.author.orcid0000-0002-1527-0738-
Appears in Collections:FCTUC Física - Artigos em Revistas Internacionais
FCTUC Ciências da Vida - Artigos em Revistas Internacionais
FCTUC Química - Artigos em Revistas Internacionais
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