Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes

Autores
Pellegrino, Juan; Gaviglio, Carina del Valle; Milstein, David; Doctorovich, Fabio
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The electrochemistry of the {RhNO}8 complexes [Rh(PCPtBu)(NO)][BF4] (1+), [Rh(PCPtBuCH2)(NO)][BF4] (2+), and Rh(PCPtBu)(NO)Cl (3) was studied. Both four-coordinate complexes 1+ and 2+ exhibit a reversible reduction within the CH2Cl2 solvent window. Nevertheless, the chemical or electrochemical reduction of 1+ and 2+ in CH2Cl2 led to the formation of the five- coordinate {RhNO}8 complexes 3 and Rh(PCPtBuCH2)(NO)Cl (4), respectively, through chloride abstraction from CH2Cl2 by the one-electron-reduced {RhNO}9 species [Rh(PCPtBu)(NO)]• (1•) and [Rh(PCPtBuCH2)(NO)]• (2•), as has been observed for many other 17-electron paramagnetic complexes. The new complex 4 was fully characterized by multinuclear NMR techniques, IR, X-ray diffraction, CV, UV−vis, and elemental analysis. On the other hand, the five-coordinate complexes 3 and 4 show only one irreversible oxidation in CH2Cl2 and two irreversible reductions in THF. The {RhNO}9 complex 1• could be obtained quantitatively by one-electron reduction of 1+ with cobaltocene in nonchlorinated solvents and was characterized by IR, EPR, and 1H NMR in solution. Activation of carbon−halogen bonds by complex 1• was observed by studying the reactivity of 1• with some aryl halides, giving in all cases the {RhNO}8 Rh(PCPtBu)(NO)X (X = Cl−, 3, or X = I−, 6) as the only rhodium complex, while a complex with coordination of the aryl moiety was not observed as a stable final product in any case. The fate of the aryl organic radicals could be determined in some cases. In addition, DFT calculations were performed to elucidate the electronic structure of 1• and to support the observed reactivity.
Fil: Pellegrino, Juan. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina
Fil: Gaviglio, Carina del Valle. Universidad de Buenos Aires; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Milstein, David . The Weizmann Institute of Science; Israel
Fil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina
Materia
Rhodium
Nitrosyl
Electrochemistry
Paramagnetic
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/8111
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/8111
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexesPellegrino, JuanGaviglio, Carina del ValleMilstein, David Doctorovich, FabioRhodiumNitrosylElectrochemistryParamagnetichttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The electrochemistry of the {RhNO}8 complexes [Rh(PCPtBu)(NO)][BF4] (1+), [Rh(PCPtBuCH2)(NO)][BF4] (2+), and Rh(PCPtBu)(NO)Cl (3) was studied. Both four-coordinate complexes 1+ and 2+ exhibit a reversible reduction within the CH2Cl2 solvent window. Nevertheless, the chemical or electrochemical reduction of 1+ and 2+ in CH2Cl2 led to the formation of the five- coordinate {RhNO}8 complexes 3 and Rh(PCPtBuCH2)(NO)Cl (4), respectively, through chloride abstraction from CH2Cl2 by the one-electron-reduced {RhNO}9 species [Rh(PCPtBu)(NO)]• (1•) and [Rh(PCPtBuCH2)(NO)]• (2•), as has been observed for many other 17-electron paramagnetic complexes. The new complex 4 was fully characterized by multinuclear NMR techniques, IR, X-ray diffraction, CV, UV−vis, and elemental analysis. On the other hand, the five-coordinate complexes 3 and 4 show only one irreversible oxidation in CH2Cl2 and two irreversible reductions in THF. The {RhNO}9 complex 1• could be obtained quantitatively by one-electron reduction of 1+ with cobaltocene in nonchlorinated solvents and was characterized by IR, EPR, and 1H NMR in solution. Activation of carbon−halogen bonds by complex 1• was observed by studying the reactivity of 1• with some aryl halides, giving in all cases the {RhNO}8 Rh(PCPtBu)(NO)X (X = Cl−, 3, or X = I−, 6) as the only rhodium complex, while a complex with coordination of the aryl moiety was not observed as a stable final product in any case. The fate of the aryl organic radicals could be determined in some cases. In addition, DFT calculations were performed to elucidate the electronic structure of 1• and to support the observed reactivity.Fil: Pellegrino, Juan. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; ArgentinaFil: Gaviglio, Carina del Valle. Universidad de Buenos Aires; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Milstein, David . The Weizmann Institute of Science; IsraelFil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; ArgentinaAmerican Chemical Society2013-10-31info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/8111Pellegrino, Juan; Gaviglio, Carina del Valle; Milstein, David ; Doctorovich, Fabio; Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes; American Chemical Society; Organometallics; 32; 21; 31-10-2013; 6555-65640276-7333enginfo:eu-repo/semantics/altIdentifier/doi/ 10.1021/om4008746info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/om4008746info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:59:46Zoai:ri.conicet.gov.ar:11336/8111instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:59:46.967CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes
title Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes
spellingShingle Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes
Pellegrino, Juan
Rhodium
Nitrosyl
Electrochemistry
Paramagnetic
title_short Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes
title_full Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes
title_fullStr Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes
title_full_unstemmed Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes
title_sort Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes
dc.creator.none.fl_str_mv Pellegrino, Juan
Gaviglio, Carina del Valle
Milstein, David
Doctorovich, Fabio
author Pellegrino, Juan
author_facet Pellegrino, Juan
Gaviglio, Carina del Valle
Milstein, David
Doctorovich, Fabio
author_role author
author2 Gaviglio, Carina del Valle
Milstein, David
Doctorovich, Fabio
author2_role author
author
author
dc.subject.none.fl_str_mv Rhodium
Nitrosyl
Electrochemistry
Paramagnetic
topic Rhodium
Nitrosyl
Electrochemistry
Paramagnetic
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The electrochemistry of the {RhNO}8 complexes [Rh(PCPtBu)(NO)][BF4] (1+), [Rh(PCPtBuCH2)(NO)][BF4] (2+), and Rh(PCPtBu)(NO)Cl (3) was studied. Both four-coordinate complexes 1+ and 2+ exhibit a reversible reduction within the CH2Cl2 solvent window. Nevertheless, the chemical or electrochemical reduction of 1+ and 2+ in CH2Cl2 led to the formation of the five- coordinate {RhNO}8 complexes 3 and Rh(PCPtBuCH2)(NO)Cl (4), respectively, through chloride abstraction from CH2Cl2 by the one-electron-reduced {RhNO}9 species [Rh(PCPtBu)(NO)]• (1•) and [Rh(PCPtBuCH2)(NO)]• (2•), as has been observed for many other 17-electron paramagnetic complexes. The new complex 4 was fully characterized by multinuclear NMR techniques, IR, X-ray diffraction, CV, UV−vis, and elemental analysis. On the other hand, the five-coordinate complexes 3 and 4 show only one irreversible oxidation in CH2Cl2 and two irreversible reductions in THF. The {RhNO}9 complex 1• could be obtained quantitatively by one-electron reduction of 1+ with cobaltocene in nonchlorinated solvents and was characterized by IR, EPR, and 1H NMR in solution. Activation of carbon−halogen bonds by complex 1• was observed by studying the reactivity of 1• with some aryl halides, giving in all cases the {RhNO}8 Rh(PCPtBu)(NO)X (X = Cl−, 3, or X = I−, 6) as the only rhodium complex, while a complex with coordination of the aryl moiety was not observed as a stable final product in any case. The fate of the aryl organic radicals could be determined in some cases. In addition, DFT calculations were performed to elucidate the electronic structure of 1• and to support the observed reactivity.
Fil: Pellegrino, Juan. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina
Fil: Gaviglio, Carina del Valle. Universidad de Buenos Aires; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Milstein, David . The Weizmann Institute of Science; Israel
Fil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina
description The electrochemistry of the {RhNO}8 complexes [Rh(PCPtBu)(NO)][BF4] (1+), [Rh(PCPtBuCH2)(NO)][BF4] (2+), and Rh(PCPtBu)(NO)Cl (3) was studied. Both four-coordinate complexes 1+ and 2+ exhibit a reversible reduction within the CH2Cl2 solvent window. Nevertheless, the chemical or electrochemical reduction of 1+ and 2+ in CH2Cl2 led to the formation of the five- coordinate {RhNO}8 complexes 3 and Rh(PCPtBuCH2)(NO)Cl (4), respectively, through chloride abstraction from CH2Cl2 by the one-electron-reduced {RhNO}9 species [Rh(PCPtBu)(NO)]• (1•) and [Rh(PCPtBuCH2)(NO)]• (2•), as has been observed for many other 17-electron paramagnetic complexes. The new complex 4 was fully characterized by multinuclear NMR techniques, IR, X-ray diffraction, CV, UV−vis, and elemental analysis. On the other hand, the five-coordinate complexes 3 and 4 show only one irreversible oxidation in CH2Cl2 and two irreversible reductions in THF. The {RhNO}9 complex 1• could be obtained quantitatively by one-electron reduction of 1+ with cobaltocene in nonchlorinated solvents and was characterized by IR, EPR, and 1H NMR in solution. Activation of carbon−halogen bonds by complex 1• was observed by studying the reactivity of 1• with some aryl halides, giving in all cases the {RhNO}8 Rh(PCPtBu)(NO)X (X = Cl−, 3, or X = I−, 6) as the only rhodium complex, while a complex with coordination of the aryl moiety was not observed as a stable final product in any case. The fate of the aryl organic radicals could be determined in some cases. In addition, DFT calculations were performed to elucidate the electronic structure of 1• and to support the observed reactivity.
publishDate 2013
dc.date.none.fl_str_mv 2013-10-31
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/8111
Pellegrino, Juan; Gaviglio, Carina del Valle; Milstein, David ; Doctorovich, Fabio; Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes; American Chemical Society; Organometallics; 32; 21; 31-10-2013; 6555-6564
0276-7333
url http://hdl.handle.net/11336/8111
identifier_str_mv Pellegrino, Juan; Gaviglio, Carina del Valle; Milstein, David ; Doctorovich, Fabio; Electron transfer behavior of pincer-type {RhNO}8 complexes: Spectroscopic characterization and reactivity of paramagnetic {RhNO}9 complexes; American Chemical Society; Organometallics; 32; 21; 31-10-2013; 6555-6564
0276-7333
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/ 10.1021/om4008746
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/om4008746
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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