Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

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Autor(a) principal: Vivas-Reyes,R.
Data de Publicação: 2008
Outros Autores: Aria,A.
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Eclética Química
Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-46702008000300010
Resumo: Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.
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spelling Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra dataDFT CalculationsNMRSnRR'X groupselectronegativityhardnesssoftnessQuantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.Fundação Editora da Universidade Estadual Paulista Júlio de Mesquita Filho - UNESP2008-01-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-46702008000300010Eclética Química v.33 n.3 2008reponame:Eclética Químicainstname:Universidade Estadual Paulista Júlio de Mesquita Filho (UNESP)instacron:UNESP10.1590/S0100-46702008000300010info:eu-repo/semantics/openAccessVivas-Reyes,R.Aria,A.eng2008-10-28T00:00:00Zoai:scielo:S0100-46702008000300010Revistahttp://revista.iq.unesp.br/ojs/index.php/ecletica/PUBhttps://revista.iq.unesp.br/ojs/index.php/ecletica/oaiecletica@ctrlk.com.br||ecletica@iq.unesp.br1678-46181678-4618opendoar:2008-10-28T00:00Eclética Química - Universidade Estadual Paulista Júlio de Mesquita Filho (UNESP)false
dc.title.none.fl_str_mv Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data
title Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data
spellingShingle Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data
Vivas-Reyes,R.
DFT Calculations
NMR
SnRR'X groups
electronegativity
hardness
softness
title_short Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data
title_full Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data
title_fullStr Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data
title_full_unstemmed Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data
title_sort Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data
author Vivas-Reyes,R.
author_facet Vivas-Reyes,R.
Aria,A.
author_role author
author2 Aria,A.
author2_role author
dc.contributor.author.fl_str_mv Vivas-Reyes,R.
Aria,A.
dc.subject.por.fl_str_mv DFT Calculations
NMR
SnRR'X groups
electronegativity
hardness
softness
topic DFT Calculations
NMR
SnRR'X groups
electronegativity
hardness
softness
description Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.
publishDate 2008
dc.date.none.fl_str_mv 2008-01-01
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-46702008000300010
url http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-46702008000300010
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 10.1590/S0100-46702008000300010
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv text/html
dc.publisher.none.fl_str_mv Fundação Editora da Universidade Estadual Paulista Júlio de Mesquita Filho - UNESP
publisher.none.fl_str_mv Fundação Editora da Universidade Estadual Paulista Júlio de Mesquita Filho - UNESP
dc.source.none.fl_str_mv Eclética Química v.33 n.3 2008
reponame:Eclética Química
instname:Universidade Estadual Paulista Júlio de Mesquita Filho (UNESP)
instacron:UNESP
instname_str Universidade Estadual Paulista Júlio de Mesquita Filho (UNESP)
instacron_str UNESP
institution UNESP
reponame_str Eclética Química
collection Eclética Química
repository.name.fl_str_mv Eclética Química - Universidade Estadual Paulista Júlio de Mesquita Filho (UNESP)
repository.mail.fl_str_mv ecletica@ctrlk.com.br||ecletica@iq.unesp.br
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