Utilize este identificador para referenciar este registo: https://hdl.handle.net/10316/12343
Título: Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shifts
Autor: Justino, Licínia L. G. 
Ramos, M. Luísa 
Kaupp, Martin 
Burrows, Hugh D. 
Fiolhais, Carlos 
Gil, Victor M. S. 
Data: 2009
Editora: Royal Society of Chemistry
Citação: Dalton Transactions. (2009) 9735-9745
Resumo: The DFT B3LYP/SBKJC method has been used to calculate the gas-phase optimized geometries of the glycolate oxoperoxo vanadium(V) complexes [V2O2(OO)2(gly)2]2-, [V2O3(OO)(gly)2]2- and [VO(OO)(gly)(H2O)]-. The 51V, 17O, 13C and 1H chemical shifts have been calculated for the theoretical geometries in all-electron DFT calculations at the UDFT-IGLO-PW91 level and have been subsequently compared with the experimental chemical shifts in solution. In spite of being applied to the isolated molecules, the calculations allowed satisfactory reproduction of the multinuclear NMR solution chemical shifts of the complexes, suggesting that the theoretical structures are probably close to those in solution. The effects of structural changes on the 51V and 17O NMR chemical shifts have been analysed using the referred computational methodologies for one of the glycolate complexes and for several small molecules taken as models. These calculations showed that structural modifications far from the metal nucleus do not significantly affect the metal chemical shift. This finding explains why it is possible to establish reference scales that correlate the type of complex (type of metal centre associated with a certain type of ligand) with its typical region of metal chemical shifts. It has also been found that the VO bond length is the dominant geometrical parameter determining both 51V and the oxo 17O in this kind of complex
URI: https://hdl.handle.net/10316/12343
ISSN: 1477-9226
DOI: 10.1039/b910033d
Direitos: openAccess
Aparece nas coleções:FCTUC Física - Artigos em Revistas Internacionais

Ficheiros deste registo:
Ficheiro Descrição TamanhoFormato
Density functional theory study of the oxoperoxo vanadium.pdf448.19 kBAdobe PDFVer/Abrir
Mostrar registo em formato completo

Citações SCOPUSTM   

26
Visto em 9/nov/2022

Citações WEB OF SCIENCETM
5

29
Visto em 2/nov/2024

Visualizações de página 50

558
Visto em 29/out/2024

Downloads

382
Visto em 29/out/2024

Google ScholarTM

Verificar

Altmetric

Altmetric


Todos os registos no repositório estão protegidos por leis de copyright, com todos os direitos reservados.