Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shifts
Autor(a) principal: | |
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Data de Publicação: | 2009 |
Outros Autores: | , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10316/12343 https://doi.org/10.1039/b910033d |
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 |
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Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shiftsThe 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 complexRoyal Society of Chemistry2009info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/12343http://hdl.handle.net/10316/12343https://doi.org/10.1039/b910033dengDalton Transactions. (2009) 9735-97451477-9226Justino, Licínia L. G.Ramos, M. LuísaKaupp, MartinBurrows, Hugh D.Fiolhais, CarlosGil, Victor M. S.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2021-05-25T08:13:41Zoai:estudogeral.uc.pt:10316/12343Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:59:55.604964Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shifts |
title |
Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shifts |
spellingShingle |
Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shifts Justino, Licínia L. G. |
title_short |
Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shifts |
title_full |
Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shifts |
title_fullStr |
Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shifts |
title_full_unstemmed |
Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shifts |
title_sort |
Density functional theory study of the oxoperoxo vanadium(V) complexes of glycolic acid. Structural correlations with NMR chemical shifts |
author |
Justino, Licínia L. G. |
author_facet |
Justino, Licínia L. G. Ramos, M. Luísa Kaupp, Martin Burrows, Hugh D. Fiolhais, Carlos Gil, Victor M. S. |
author_role |
author |
author2 |
Ramos, M. Luísa Kaupp, Martin Burrows, Hugh D. Fiolhais, Carlos Gil, Victor M. S. |
author2_role |
author author author author author |
dc.contributor.author.fl_str_mv |
Justino, Licínia L. G. Ramos, M. Luísa Kaupp, Martin Burrows, Hugh D. Fiolhais, Carlos Gil, Victor M. S. |
description |
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 |
publishDate |
2009 |
dc.date.none.fl_str_mv |
2009 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10316/12343 http://hdl.handle.net/10316/12343 https://doi.org/10.1039/b910033d |
url |
http://hdl.handle.net/10316/12343 https://doi.org/10.1039/b910033d |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Dalton Transactions. (2009) 9735-9745 1477-9226 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Royal Society of Chemistry |
publisher.none.fl_str_mv |
Royal Society of Chemistry |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
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1799133889477738496 |