Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms

Detalhes bibliográficos
Autor(a) principal: Rocha,Willian R.
Data de Publicação: 2002
Outros Autores: Duarte,Leopoldo W. M., Almeida,Wagner B. De, Caliman,Vinicius
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Journal of the Brazilian Chemical Society (Online)
Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532002000500009
Resumo: The synthesis of two new arsadiphospholes of formula (AsP2C2Bu t2 )CH(SiMe3)2, from 4-arsa-1,2-diphosphacyclopentadienyl and 2-arsa-1,4-diphosphacyclopentadienyl ring anions are reported together with their characterization by 31P NMR. Ab initio calculations at the MP2/6-31G(d) level of theory were carried out to investigate the energy barrier for pyramidal inversion about the pyramidal P and As atoms, relative stability and aromaticity character of all possible isomers in the gas phase. The thermodynamic isomers distribution is in agreement with the experimental results. The inversion barrier at the sp³ phosphorus compared to the inversion barrier found for the arsenic atom is low. This fact is directly related with the aromaticity of the rings and shows the preference of the side group for the phosphorus atom, which leads to a more aromatic ring structure. The aromaticity character found for three isomers containing a sp³-phosphorus is greater if compared with that of 1,2,4-triphosphole synthesized previously. The effects of bulky R substituents on the aromaticity and on the energy barrier for pyramidal inversion are also discussed.
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spelling Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atomsarsadiphospholessynthesis31P NMRaromaticityab initio calculationsThe synthesis of two new arsadiphospholes of formula (AsP2C2Bu t2 )CH(SiMe3)2, from 4-arsa-1,2-diphosphacyclopentadienyl and 2-arsa-1,4-diphosphacyclopentadienyl ring anions are reported together with their characterization by 31P NMR. Ab initio calculations at the MP2/6-31G(d) level of theory were carried out to investigate the energy barrier for pyramidal inversion about the pyramidal P and As atoms, relative stability and aromaticity character of all possible isomers in the gas phase. The thermodynamic isomers distribution is in agreement with the experimental results. The inversion barrier at the sp³ phosphorus compared to the inversion barrier found for the arsenic atom is low. This fact is directly related with the aromaticity of the rings and shows the preference of the side group for the phosphorus atom, which leads to a more aromatic ring structure. The aromaticity character found for three isomers containing a sp³-phosphorus is greater if compared with that of 1,2,4-triphosphole synthesized previously. The effects of bulky R substituents on the aromaticity and on the energy barrier for pyramidal inversion are also discussed.Sociedade Brasileira de Química2002-09-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532002000500009Journal of the Brazilian Chemical Society v.13 n.5 2002reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.1590/S0103-50532002000500009info:eu-repo/semantics/openAccessRocha,Willian R.Duarte,Leopoldo W. M.Almeida,Wagner B. DeCaliman,Viniciuseng2008-10-08T00:00:00Zoai:scielo:S0103-50532002000500009Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2008-10-08T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false
dc.title.none.fl_str_mv Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms
title Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms
spellingShingle Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms
Rocha,Willian R.
arsadiphospholes
synthesis
31P NMR
aromaticity
ab initio calculations
title_short Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms
title_full Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms
title_fullStr Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms
title_full_unstemmed Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms
title_sort Synthesis, Characterization and Theoretical Calculations of Novel Five Membered Rings Containing Phosphorus and Arsenic Atoms
author Rocha,Willian R.
author_facet Rocha,Willian R.
Duarte,Leopoldo W. M.
Almeida,Wagner B. De
Caliman,Vinicius
author_role author
author2 Duarte,Leopoldo W. M.
Almeida,Wagner B. De
Caliman,Vinicius
author2_role author
author
author
dc.contributor.author.fl_str_mv Rocha,Willian R.
Duarte,Leopoldo W. M.
Almeida,Wagner B. De
Caliman,Vinicius
dc.subject.por.fl_str_mv arsadiphospholes
synthesis
31P NMR
aromaticity
ab initio calculations
topic arsadiphospholes
synthesis
31P NMR
aromaticity
ab initio calculations
description The synthesis of two new arsadiphospholes of formula (AsP2C2Bu t2 )CH(SiMe3)2, from 4-arsa-1,2-diphosphacyclopentadienyl and 2-arsa-1,4-diphosphacyclopentadienyl ring anions are reported together with their characterization by 31P NMR. Ab initio calculations at the MP2/6-31G(d) level of theory were carried out to investigate the energy barrier for pyramidal inversion about the pyramidal P and As atoms, relative stability and aromaticity character of all possible isomers in the gas phase. The thermodynamic isomers distribution is in agreement with the experimental results. The inversion barrier at the sp³ phosphorus compared to the inversion barrier found for the arsenic atom is low. This fact is directly related with the aromaticity of the rings and shows the preference of the side group for the phosphorus atom, which leads to a more aromatic ring structure. The aromaticity character found for three isomers containing a sp³-phosphorus is greater if compared with that of 1,2,4-triphosphole synthesized previously. The effects of bulky R substituents on the aromaticity and on the energy barrier for pyramidal inversion are also discussed.
publishDate 2002
dc.date.none.fl_str_mv 2002-09-01
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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dc.identifier.uri.fl_str_mv http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532002000500009
url http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532002000500009
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 10.1590/S0103-50532002000500009
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 Sociedade Brasileira de Química
publisher.none.fl_str_mv Sociedade Brasileira de Química
dc.source.none.fl_str_mv Journal of the Brazilian Chemical Society v.13 n.5 2002
reponame:Journal of the Brazilian Chemical Society (Online)
instname:Sociedade Brasileira de Química (SBQ)
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instname_str Sociedade Brasileira de Química (SBQ)
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reponame_str Journal of the Brazilian Chemical Society (Online)
collection Journal of the Brazilian Chemical Society (Online)
repository.name.fl_str_mv Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)
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