Iron complexes containing electrochemically active diazocycle-bis(di-tert-butyl-phenol) ligands
Autor(a) principal: | |
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Data de Publicação: | 2014 |
Outros Autores: | , , , , , , |
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=S0103-50532014000600009 |
Resumo: | Four N, O-donor ligands built on diazocycle platforms and containing bis(di-tert-butyl-phenol) as pendant arms were employed in the synthesis of iron(III) complexes, resulting in four mononuclear and one dinuclear complexes. The ligands are distinct with respect to the diazocycle backbone: piperazine (H2L1), diazepane/homopiperazine (H2L2), hexahydropyrimidine (H2L3) or hexahydropyrimidin-5-ol (H3L4). The molecular structure of compounds [FeL2Cl], 2, and [Fe2(L4)(HL4)Cl], 4, were solved by single crystal X-ray diffraction analysis. Electrochemical data showed that, in addition to the electrochemical process centered on the metal, the compounds show ligand-centered redox processes. Coulometric studies with concomitant UV-Vis analyses confirmed that compound 2 generated the phenoxyl species, while electron paramagnetic resonance (EPR) spectroscopy confirmed the radical formation for compounds 2, 4 and 5. Of interest was the observation that the compound in which the ligand can be oxidized easiest is the one where the metal center shows the lowest Lewis acidity. |
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Iron complexes containing electrochemically active diazocycle-bis(di-tert-butyl-phenol) ligandsphenoxyl radicaliron compoundsdiazocycletert-butylphenolnon-innocent ligandFour N, O-donor ligands built on diazocycle platforms and containing bis(di-tert-butyl-phenol) as pendant arms were employed in the synthesis of iron(III) complexes, resulting in four mononuclear and one dinuclear complexes. The ligands are distinct with respect to the diazocycle backbone: piperazine (H2L1), diazepane/homopiperazine (H2L2), hexahydropyrimidine (H2L3) or hexahydropyrimidin-5-ol (H3L4). The molecular structure of compounds [FeL2Cl], 2, and [Fe2(L4)(HL4)Cl], 4, were solved by single crystal X-ray diffraction analysis. Electrochemical data showed that, in addition to the electrochemical process centered on the metal, the compounds show ligand-centered redox processes. Coulometric studies with concomitant UV-Vis analyses confirmed that compound 2 generated the phenoxyl species, while electron paramagnetic resonance (EPR) spectroscopy confirmed the radical formation for compounds 2, 4 and 5. Of interest was the observation that the compound in which the ligand can be oxidized easiest is the one where the metal center shows the lowest Lewis acidity.Sociedade Brasileira de Química2014-06-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532014000600009Journal of the Brazilian Chemical Society v.25 n.6 2014reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.5935/0103-5053.20140078info:eu-repo/semantics/openAccessMendes,Luísa L.Fernandes,ChristianeFranco,Roberto W. A.Lube,Leonardo M.Wei,Sheng-HsuanReibenspies,Joseph H.Darensbourg,Donald J.Horn Jr.,Adolfoeng2014-07-01T00:00:00Zoai:scielo:S0103-50532014000600009Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2014-07-01T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false |
dc.title.none.fl_str_mv |
Iron complexes containing electrochemically active diazocycle-bis(di-tert-butyl-phenol) ligands |
title |
Iron complexes containing electrochemically active diazocycle-bis(di-tert-butyl-phenol) ligands |
spellingShingle |
Iron complexes containing electrochemically active diazocycle-bis(di-tert-butyl-phenol) ligands Mendes,Luísa L. phenoxyl radical iron compounds diazocycle tert-butylphenol non-innocent ligand |
title_short |
Iron complexes containing electrochemically active diazocycle-bis(di-tert-butyl-phenol) ligands |
title_full |
Iron complexes containing electrochemically active diazocycle-bis(di-tert-butyl-phenol) ligands |
title_fullStr |
Iron complexes containing electrochemically active diazocycle-bis(di-tert-butyl-phenol) ligands |
title_full_unstemmed |
Iron complexes containing electrochemically active diazocycle-bis(di-tert-butyl-phenol) ligands |
title_sort |
Iron complexes containing electrochemically active diazocycle-bis(di-tert-butyl-phenol) ligands |
author |
Mendes,Luísa L. |
author_facet |
Mendes,Luísa L. Fernandes,Christiane Franco,Roberto W. A. Lube,Leonardo M. Wei,Sheng-Hsuan Reibenspies,Joseph H. Darensbourg,Donald J. Horn Jr.,Adolfo |
author_role |
author |
author2 |
Fernandes,Christiane Franco,Roberto W. A. Lube,Leonardo M. Wei,Sheng-Hsuan Reibenspies,Joseph H. Darensbourg,Donald J. Horn Jr.,Adolfo |
author2_role |
author author author author author author author |
dc.contributor.author.fl_str_mv |
Mendes,Luísa L. Fernandes,Christiane Franco,Roberto W. A. Lube,Leonardo M. Wei,Sheng-Hsuan Reibenspies,Joseph H. Darensbourg,Donald J. Horn Jr.,Adolfo |
dc.subject.por.fl_str_mv |
phenoxyl radical iron compounds diazocycle tert-butylphenol non-innocent ligand |
topic |
phenoxyl radical iron compounds diazocycle tert-butylphenol non-innocent ligand |
description |
Four N, O-donor ligands built on diazocycle platforms and containing bis(di-tert-butyl-phenol) as pendant arms were employed in the synthesis of iron(III) complexes, resulting in four mononuclear and one dinuclear complexes. The ligands are distinct with respect to the diazocycle backbone: piperazine (H2L1), diazepane/homopiperazine (H2L2), hexahydropyrimidine (H2L3) or hexahydropyrimidin-5-ol (H3L4). The molecular structure of compounds [FeL2Cl], 2, and [Fe2(L4)(HL4)Cl], 4, were solved by single crystal X-ray diffraction analysis. Electrochemical data showed that, in addition to the electrochemical process centered on the metal, the compounds show ligand-centered redox processes. Coulometric studies with concomitant UV-Vis analyses confirmed that compound 2 generated the phenoxyl species, while electron paramagnetic resonance (EPR) spectroscopy confirmed the radical formation for compounds 2, 4 and 5. Of interest was the observation that the compound in which the ligand can be oxidized easiest is the one where the metal center shows the lowest Lewis acidity. |
publishDate |
2014 |
dc.date.none.fl_str_mv |
2014-06-01 |
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=S0103-50532014000600009 |
url |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532014000600009 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.5935/0103-5053.20140078 |
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.25 n.6 2014 reponame:Journal of the Brazilian Chemical Society (Online) instname:Sociedade Brasileira de Química (SBQ) instacron:SBQ |
instname_str |
Sociedade Brasileira de Química (SBQ) |
instacron_str |
SBQ |
institution |
SBQ |
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) |
repository.mail.fl_str_mv |
||office@jbcs.sbq.org.br |
_version_ |
1750318176117194752 |