Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridin...

Autores: Crespi, Ayelen Florencia; Sanchez, Veronica Muriel; Vega, Daniel Alberto; Pérez, Ana Laura; Brondino, Carlos Dante; Garro Linck, Yamila; Hodgkinson, Paul; Rodríguez Castellón, Enrique; Lazaro Martinez, Juan Manuel
Año de publicación: 2021
Idioma: inglés
Tipo de recurso: artículo
Estado: versión publicada
Descripción: The complex chemical functionalization of aldehyde moieties in Cu(ii)- and Co(ii)-pyridinecarboxaldehyde complexes was studied. X-ray studies demonstrated that the aldehyde group (RCHO) of the four pyridine molecules is converted to dihydrogen ortho ester (RC(OCH3)(OH)2) and hemiacetal (RCH(OH)(OCH3)) moieties in both 4-pyridinecarboxaldehyde copper and cobalt complexes. In contrast, the aldehyde group is retained when the 3-pyridinecarboxaldehyde ligand is complexed with cobalt. In the different copper complexes, similar paramagnetic 1H resonance lines were obtained in the solid state; however, the connectivity with the carbon structure and the 1H vicinities were done with 2D 1H-13C HETCOR, 1H-1H SQ/DQ and proton spin diffusion (PSD) experiments. The strong paramagnetic effect exerted by the cobalt center prevented the observation of 13C NMR signals and chemical information could only be obtained from X-ray experiments. 2D PSD experiments in the solid state were useful for the proton assignments in both Cu(ii) complexes. The combination of X-ray crystallography experiments with DFT calculations together with the experimental results obtained from EPR and solid-state NMR allowed the assignment of NMR signals in pyridinecarboxaldehyde ligands coordinated with copper ions. In cases where the crystallographic information was not available, as in the case of the 3-pyridinecarboxaldehyde Cu(ii) complex, the combination of these techniques allowed not only the assignment of NMR signals but also the study of the functionalization of the substituent group.
Fil: Crespi, Ayelen Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Metabolismo del Fármaco. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Metabolismo del Fármaco; Argentina
Fil: Sanchez, Veronica Muriel. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Simulación Computacional para Aplicaciones Tecnológicas; Argentina
Fil: Vega, Daniel Alberto. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Pérez, Ana Laura. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Brondino, Carlos Dante. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Garro Linck, Yamila. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomia y Física. Sección Física. Grupo de Resonancia Magnética Nuclear; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: Hodgkinson, Paul. University Of Durham. Dep.of Chemistry; Reino Unido
Fil: Rodríguez Castellón, Enrique. Universidad de Málaga. Facultad de Ciencias; España
Fil: Lazaro Martinez, Juan Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Metabolismo del Fármaco. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Metabolismo del Fármaco; Argentina
Materia: Solid-state NMR
X-ray
Copper Complexes
EPR
Nivel de accesibilidad: acceso abierto
Condiciones de uso: https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
Institución: Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador: oai:ri.conicet.gov.ar:11336/182369

Acceder

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network_acronym_str	CONICETDig
repository_id_str	3498
network_name_str	CONICET Digital (CONICET)
spelling	Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexesCrespi, Ayelen FlorenciaSanchez, Veronica MurielVega, Daniel AlbertoPérez, Ana LauraBrondino, Carlos DanteGarro Linck, YamilaHodgkinson, PaulRodríguez Castellón, EnriqueLazaro Martinez, Juan ManuelSolid-state NMRX-rayCopper ComplexesEPRhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The complex chemical functionalization of aldehyde moieties in Cu(ii)- and Co(ii)-pyridinecarboxaldehyde complexes was studied. X-ray studies demonstrated that the aldehyde group (RCHO) of the four pyridine molecules is converted to dihydrogen ortho ester (RC(OCH3)(OH)2) and hemiacetal (RCH(OH)(OCH3)) moieties in both 4-pyridinecarboxaldehyde copper and cobalt complexes. In contrast, the aldehyde group is retained when the 3-pyridinecarboxaldehyde ligand is complexed with cobalt. In the different copper complexes, similar paramagnetic 1H resonance lines were obtained in the solid state; however, the connectivity with the carbon structure and the 1H vicinities were done with 2D 1H-13C HETCOR, 1H-1H SQ/DQ and proton spin diffusion (PSD) experiments. The strong paramagnetic effect exerted by the cobalt center prevented the observation of 13C NMR signals and chemical information could only be obtained from X-ray experiments. 2D PSD experiments in the solid state were useful for the proton assignments in both Cu(ii) complexes. The combination of X-ray crystallography experiments with DFT calculations together with the experimental results obtained from EPR and solid-state NMR allowed the assignment of NMR signals in pyridinecarboxaldehyde ligands coordinated with copper ions. In cases where the crystallographic information was not available, as in the case of the 3-pyridinecarboxaldehyde Cu(ii) complex, the combination of these techniques allowed not only the assignment of NMR signals but also the study of the functionalization of the substituent group.Fil: Crespi, Ayelen Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Metabolismo del Fármaco. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Metabolismo del Fármaco; ArgentinaFil: Sanchez, Veronica Muriel. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Simulación Computacional para Aplicaciones Tecnológicas; ArgentinaFil: Vega, Daniel Alberto. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Pérez, Ana Laura. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Brondino, Carlos Dante. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; ArgentinaFil: Garro Linck, Yamila. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomia y Física. Sección Física. Grupo de Resonancia Magnética Nuclear; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; ArgentinaFil: Hodgkinson, Paul. University Of Durham. Dep.of Chemistry; Reino UnidoFil: Rodríguez Castellón, Enrique. Universidad de Málaga. Facultad de Ciencias; EspañaFil: Lazaro Martinez, Juan Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Metabolismo del Fármaco. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Metabolismo del Fármaco; ArgentinaThe Royal Society of Chemistry2021-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/182369Crespi, Ayelen Florencia; Sanchez, Veronica Muriel; Vega, Daniel Alberto; Pérez, Ana Laura; Brondino, Carlos Dante; et al.; Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes; The Royal Society of Chemistry; RSC Advances; 11; 33; 6-2021; 1-162046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/d1ra02512kinfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2021/RA/D1RA02512Kinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:24:55Zoai:ri.conicet.gov.ar:11336/182369instacron: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 10:24:55.339CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv	Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes
title	Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes
spellingShingle	Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes Crespi, Ayelen Florencia Solid-state NMR X-ray Copper Complexes EPR
title_short	Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes
title_full	Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes
title_fullStr	Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes
title_full_unstemmed	Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes
title_sort	Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes
dc.creator.none.fl_str_mv	Crespi, Ayelen Florencia Sanchez, Veronica Muriel Vega, Daniel Alberto Pérez, Ana Laura Brondino, Carlos Dante Garro Linck, Yamila Hodgkinson, Paul Rodríguez Castellón, Enrique Lazaro Martinez, Juan Manuel
author	Crespi, Ayelen Florencia
author_facet	Crespi, Ayelen Florencia Sanchez, Veronica Muriel Vega, Daniel Alberto Pérez, Ana Laura Brondino, Carlos Dante Garro Linck, Yamila Hodgkinson, Paul Rodríguez Castellón, Enrique Lazaro Martinez, Juan Manuel
author_role	author
author2	Sanchez, Veronica Muriel Vega, Daniel Alberto Pérez, Ana Laura Brondino, Carlos Dante Garro Linck, Yamila Hodgkinson, Paul Rodríguez Castellón, Enrique Lazaro Martinez, Juan Manuel
author2_role	author author author author author author author author
dc.subject.none.fl_str_mv	Solid-state NMR X-ray Copper Complexes EPR
topic	Solid-state NMR X-ray Copper Complexes EPR
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 complex chemical functionalization of aldehyde moieties in Cu(ii)- and Co(ii)-pyridinecarboxaldehyde complexes was studied. X-ray studies demonstrated that the aldehyde group (RCHO) of the four pyridine molecules is converted to dihydrogen ortho ester (RC(OCH3)(OH)2) and hemiacetal (RCH(OH)(OCH3)) moieties in both 4-pyridinecarboxaldehyde copper and cobalt complexes. In contrast, the aldehyde group is retained when the 3-pyridinecarboxaldehyde ligand is complexed with cobalt. In the different copper complexes, similar paramagnetic 1H resonance lines were obtained in the solid state; however, the connectivity with the carbon structure and the 1H vicinities were done with 2D 1H-13C HETCOR, 1H-1H SQ/DQ and proton spin diffusion (PSD) experiments. The strong paramagnetic effect exerted by the cobalt center prevented the observation of 13C NMR signals and chemical information could only be obtained from X-ray experiments. 2D PSD experiments in the solid state were useful for the proton assignments in both Cu(ii) complexes. The combination of X-ray crystallography experiments with DFT calculations together with the experimental results obtained from EPR and solid-state NMR allowed the assignment of NMR signals in pyridinecarboxaldehyde ligands coordinated with copper ions. In cases where the crystallographic information was not available, as in the case of the 3-pyridinecarboxaldehyde Cu(ii) complex, the combination of these techniques allowed not only the assignment of NMR signals but also the study of the functionalization of the substituent group. Fil: Crespi, Ayelen Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Metabolismo del Fármaco. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Metabolismo del Fármaco; Argentina Fil: Sanchez, Veronica Muriel. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Simulación Computacional para Aplicaciones Tecnológicas; Argentina Fil: Vega, Daniel Alberto. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina Fil: Pérez, Ana Laura. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Brondino, Carlos Dante. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina Fil: Garro Linck, Yamila. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomia y Física. Sección Física. Grupo de Resonancia Magnética Nuclear; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina Fil: Hodgkinson, Paul. University Of Durham. Dep.of Chemistry; Reino Unido Fil: Rodríguez Castellón, Enrique. Universidad de Málaga. Facultad de Ciencias; España Fil: Lazaro Martinez, Juan Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Metabolismo del Fármaco. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Metabolismo del Fármaco; Argentina
description	The complex chemical functionalization of aldehyde moieties in Cu(ii)- and Co(ii)-pyridinecarboxaldehyde complexes was studied. X-ray studies demonstrated that the aldehyde group (RCHO) of the four pyridine molecules is converted to dihydrogen ortho ester (RC(OCH3)(OH)2) and hemiacetal (RCH(OH)(OCH3)) moieties in both 4-pyridinecarboxaldehyde copper and cobalt complexes. In contrast, the aldehyde group is retained when the 3-pyridinecarboxaldehyde ligand is complexed with cobalt. In the different copper complexes, similar paramagnetic 1H resonance lines were obtained in the solid state; however, the connectivity with the carbon structure and the 1H vicinities were done with 2D 1H-13C HETCOR, 1H-1H SQ/DQ and proton spin diffusion (PSD) experiments. The strong paramagnetic effect exerted by the cobalt center prevented the observation of 13C NMR signals and chemical information could only be obtained from X-ray experiments. 2D PSD experiments in the solid state were useful for the proton assignments in both Cu(ii) complexes. The combination of X-ray crystallography experiments with DFT calculations together with the experimental results obtained from EPR and solid-state NMR allowed the assignment of NMR signals in pyridinecarboxaldehyde ligands coordinated with copper ions. In cases where the crystallographic information was not available, as in the case of the 3-pyridinecarboxaldehyde Cu(ii) complex, the combination of these techniques allowed not only the assignment of NMR signals but also the study of the functionalization of the substituent group.
publishDate	2021
dc.date.none.fl_str_mv	2021-06
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/11336/182369 Crespi, Ayelen Florencia; Sanchez, Veronica Muriel; Vega, Daniel Alberto; Pérez, Ana Laura; Brondino, Carlos Dante; et al.; Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes; The Royal Society of Chemistry; RSC Advances; 11; 33; 6-2021; 1-16 2046-2069 CONICET Digital CONICET
url	http://hdl.handle.net/11336/182369
identifier_str_mv	Crespi, Ayelen Florencia; Sanchez, Veronica Muriel; Vega, Daniel Alberto; Pérez, Ana Laura; Brondino, Carlos Dante; et al.; Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridinecarboxaldehyde complexes; The Royal Society of Chemistry; RSC Advances; 11; 33; 6-2021; 1-16 2046-2069 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/d1ra02512k info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2021/RA/D1RA02512K
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 application/pdf
dc.publisher.none.fl_str_mv	The Royal Society of Chemistry
publisher.none.fl_str_mv	The Royal Society of Chemistry
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

Paramagnetic solid-state NMR assignment and novel chemical conversion of the aldehyde group to dihydrogen: Ortho ester and hemiacetal moieties in copper(ii)- And cobalt(ii)-pyridin...

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