NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex

The reactivity of the {RhNO}9 complex [Rh(PCPtBu)(NO)] (1) with NO was studied. A disproportionation reaction takes place in which N2O is released quantitatively, while the complex Rh(PCPtBu)(NO)(NO2) (2), with coordinated nitrite, is formed. The new complex 2 was fully characterized by multinuclear...

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Detalles Bibliográficos
Autores: Gaviglio, Carina del Valle, Pellegrino, Juan, Milstein, David, Doctorovich, Fabio
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2017
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/42223
Acceso en línea:http://hdl.handle.net/11336/42223
Access Level:acceso abierto
Palabra clave:NITROSYL
NO? DESPROPORCION
NITRO LIGAND
PINCER-TYPE LIGAND
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
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network_name_str Argentina
repository_id_str
spelling NO • Disproportionation by a {RhNO} 9 Pincer-Type ComplexGaviglio, Carina del VallePellegrino, JuanMilstein, DavidDoctorovich, FabioNITROSYLNO? DESPROPORCIONNITRO LIGANDPINCER-TYPE LIGANDhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The reactivity of the {RhNO}9 complex [Rh(PCPtBu)(NO)] (1) with NO was studied. A disproportionation reaction takes place in which N2O is released quantitatively, while the complex Rh(PCPtBu)(NO)(NO2) (2), with coordinated nitrite, is formed. The new complex 2 was fully characterized by multinuclear NMR techniques, IR and X-ray diffraction. The X-ray structure reveals a square pyramidal geometry with an N-bound nitro ligand trans to the Cipso of the PCP ligand and a bent nitrosyl ligand in the apical position. IR measurement of released N2O confirms that one equivalent forms for each molecule of 1. Infrared spectroscopic experiments with 1-15NO and 14NO suggest that the reaction occurs through the intermediacy of a dinitrosyl complex. In addition, DFT calculations were performed to provide more evidence on the structure of the intermediates and to support the observed reactivity.Fil: Gaviglio, Carina del Valle. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área Investigaciones y Aplicaciones no Nucleares; ArgentinaFil: 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. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Milstein, David. Weizmann Institute of Science. Department of Organic Chemistry; 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. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaRoyal Society of Chemistry2017-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/42223Gaviglio, Carina del Valle; Pellegrino, Juan; Milstein, David; Doctorovich, Fabio; NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex; Royal Society of Chemistry; Dalton Transactions; 46; 48; 11-2017; 16878-168841477-9226CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C7DT03944Ainfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C7DT03944Ainfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2024-05-08T14:26:21Zoai:ri.conicet.gov.ar:11336/42223instacron: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:34982024-05-08 14:26:21.62CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex
title NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex
spellingShingle NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex
Gaviglio, Carina del Valle
NITROSYL
NO? DESPROPORCION
NITRO LIGAND
PINCER-TYPE LIGAND
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
title_short NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex
title_full NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex
title_fullStr NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex
title_full_unstemmed NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex
title_sort NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex
dc.creator.none.fl_str_mv Gaviglio, Carina del Valle
Pellegrino, Juan
Milstein, David
Doctorovich, Fabio
author Gaviglio, Carina del Valle
author_facet Gaviglio, Carina del Valle
Pellegrino, Juan
Milstein, David
Doctorovich, Fabio
author_role author
author2 Pellegrino, Juan
Milstein, David
Doctorovich, Fabio
author2_role author
author
author
dc.subject.none.fl_str_mv NITROSYL
NO? DESPROPORCION
NITRO LIGAND
PINCER-TYPE LIGAND
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
topic NITROSYL
NO? DESPROPORCION
NITRO LIGAND
PINCER-TYPE LIGAND
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
description The reactivity of the {RhNO}9 complex [Rh(PCPtBu)(NO)] (1) with NO was studied. A disproportionation reaction takes place in which N2O is released quantitatively, while the complex Rh(PCPtBu)(NO)(NO2) (2), with coordinated nitrite, is formed. The new complex 2 was fully characterized by multinuclear NMR techniques, IR and X-ray diffraction. The X-ray structure reveals a square pyramidal geometry with an N-bound nitro ligand trans to the Cipso of the PCP ligand and a bent nitrosyl ligand in the apical position. IR measurement of released N2O confirms that one equivalent forms for each molecule of 1. Infrared spectroscopic experiments with 1-15NO and 14NO suggest that the reaction occurs through the intermediacy of a dinitrosyl complex. In addition, DFT calculations were performed to provide more evidence on the structure of the intermediates and to support the observed reactivity.
publishDate 2017
dc.date.none.fl_str_mv 2017-11
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/11336/42223
Gaviglio, Carina del Valle; Pellegrino, Juan; Milstein, David; Doctorovich, Fabio; NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex; Royal Society of Chemistry; Dalton Transactions; 46; 48; 11-2017; 16878-16884
1477-9226
CONICET Digital
CONICET
url http://hdl.handle.net/11336/42223
identifier_str_mv Gaviglio, Carina del Valle; Pellegrino, Juan; Milstein, David; Doctorovich, Fabio; NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex; Royal Society of Chemistry; Dalton Transactions; 46; 48; 11-2017; 16878-16884
1477-9226
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/C7DT03944A
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C7DT03944A
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
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:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
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 15,812429

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