Pd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2

ilustraciones, diagramas

Autores:: Suárez Riaño, Oscar Eduardo

Tipo de recurso:

Fecha de publicación:: 2022

Institución:: Universidad Nacional de Colombia

Repositorio:: Universidad Nacional de Colombia

Idioma:: eng

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network_acronym_str	UNACIONAL2
network_name_str	Universidad Nacional de Colombia
repository_id_str
dc.title.eng.fl_str_mv	Pd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2
dc.title.translated.spa.fl_str_mv	Nanopartículas basadas en paladio estabilizadas por ligandos carbeno NHeterocíclico: Aplicación catalítica en la transformación de moléculas nitrogenadas con D2
title	Pd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2
spellingShingle	Pd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2 540 - Química y ciencias afines Paladio Níquel Nanopartículas Intercambio Isotópico de Hidrógeno Dearomatización Efecto Cinético Isotópico Inverso Ligandos Carbeno N-Heterocíclico Palladium Nickel Nanoparticles Hydrogen Isotope Exchange Dearomatization Inverse Kinetic Isotope Effect N-Heterocyclic Carbene Ligands
title_short	Pd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2
title_full	Pd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2
title_fullStr	Pd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2
title_full_unstemmed	Pd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2
title_sort	Pd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2
dc.creator.fl_str_mv	Suárez Riaño, Oscar Eduardo
dc.contributor.advisor.none.fl_str_mv	Baquero Velasco, Edwin Arley Chaudret, Bruno
dc.contributor.author.none.fl_str_mv	Suárez Riaño, Oscar Eduardo
dc.contributor.researchgroup.spa.fl_str_mv	Estado Sólido y Catálisis Ambiental
dc.contributor.orcid.spa.fl_str_mv	Oscar Suárez-Riaño [0000000190537423]
dc.subject.ddc.spa.fl_str_mv	540 - Química y ciencias afines
topic	540 - Química y ciencias afines Paladio Níquel Nanopartículas Intercambio Isotópico de Hidrógeno Dearomatización Efecto Cinético Isotópico Inverso Ligandos Carbeno N-Heterocíclico Palladium Nickel Nanoparticles Hydrogen Isotope Exchange Dearomatization Inverse Kinetic Isotope Effect N-Heterocyclic Carbene Ligands
dc.subject.proposal.spa.fl_str_mv	Paladio Níquel Nanopartículas Intercambio Isotópico de Hidrógeno Dearomatización Efecto Cinético Isotópico Inverso Ligandos Carbeno N-Heterocíclico
dc.subject.proposal.eng.fl_str_mv	Palladium Nickel Nanoparticles Hydrogen Isotope Exchange Dearomatization Inverse Kinetic Isotope Effect N-Heterocyclic Carbene Ligands
description	ilustraciones, diagramas
publishDate	2022
dc.date.issued.none.fl_str_mv	2022-10-27
dc.date.accessioned.none.fl_str_mv	2023-07-27T20:50:16Z
dc.date.available.none.fl_str_mv	2023-07-27T20:50:16Z
dc.type.spa.fl_str_mv	Trabajo de grado - Maestría
dc.type.driver.spa.fl_str_mv	info:eu-repo/semantics/masterThesis
dc.type.version.spa.fl_str_mv	info:eu-repo/semantics/acceptedVersion
dc.type.content.spa.fl_str_mv	Text
dc.type.redcol.spa.fl_str_mv	http://purl.org/redcol/resource_type/TM
status_str	acceptedVersion
dc.identifier.uri.none.fl_str_mv	https://repositorio.unal.edu.co/handle/unal/84336
dc.identifier.instname.spa.fl_str_mv	Universidad Nacional de Colombia
dc.identifier.reponame.spa.fl_str_mv	Repositorio Institucional Universidad Nacional de Colombia
dc.identifier.repourl.spa.fl_str_mv	https://repositorio.unal.edu.co/
url	https://repositorio.unal.edu.co/handle/unal/84336 https://repositorio.unal.edu.co/
identifier_str_mv	Universidad Nacional de Colombia Repositorio Institucional Universidad Nacional de Colombia
dc.language.iso.spa.fl_str_mv	eng
language	eng
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spelling	Reconocimiento 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Baquero Velasco, Edwin Arleya0215cba2df4047cc9177f789693255bChaudret, Bruno3c550616eac1bfa0d6bd87042bf18f29Suárez Riaño, Oscar Eduardob3a2ea2e0af1cdbb93191ec688904aa6Estado Sólido y Catálisis AmbientalOscar Suárez-Riaño [0000000190537423]2023-07-27T20:50:16Z2023-07-27T20:50:16Z2022-10-27https://repositorio.unal.edu.co/handle/unal/84336Universidad Nacional de ColombiaRepositorio Institucional Universidad Nacional de Colombiahttps://repositorio.unal.edu.co/ilustraciones, diagramasDeuterium-labeled compounds have been of great interest in recent years due to their diverse applications. For instance, they can be used in mechanistic studies, to alter pharmacokinetic profiles, and as internal standards in different techniques coupled to mass spectrometry. Among the different reported methods to obtain those molecules, we can highlight two: Hydrogen Isotope Exchange (HIE) reactions and dearomatization reactions using D2 as reducing agent. These processes can be catalyzed using transition metals both in homogeneous and heterogeneous fashions. In this sense, metal nanoparticles (MNPs) have appeared as a new alternative in catalysis, especially in H–H and C–H bonds activation, due to their great advantages compared to metals in their bulk conformation. Thus, N-Heterocyclic Carbene (NHC) ligands have played an important role as MNPs stabilizers due to their unique and versatile stereoelectronic properties, and their ability to form robust bonds with metals. In this line, there have been few reports about NHC-stabilized MNPs for the deuteration reactions, in which monometallic RuNPs, IrNPs, NiNPs, and bimetallic RuIrNPs and RuPtNPs were employed as nanocatalysts using different lipophilic and water-soluble substrates (amino acids). Their usual selectivities found in the deuteration of the substrates are mainly towards positions close to heteroatoms such as nitrogen. However, aromatic rings reduction still remains a major drawback in H/D exchange reactions, especially when bioactive molecules like amino acids are used. In this work we present the synthesis of monometallic PdNPs, NiNPs, and bimetallic PdNiNPs stabilized by either lipo- or water-soluble NHC ligands. The obtained MNPs were characterized by state-of-the-art techniques such as Transmission Electron Microscopy (TEM), HighResolution TEM coupled to Energy Dispersive X-Ray spectroscopy, Attenuated Total Reflectance Infrared spectroscopy, Solid-State Nuclear Magnetic Resonance, and X-Ray Photoelectron Spectroscopy. These MNPs were found to disperse in both organic and aqueous media because of the stabilization and coordination of adequate NHC ligands to the surface with sizes ranging from 1.8 to 2.9 nm. They were tested as nanocatalysts in dearomatization and HIE reactions over different lipophilic (pyridine, 2-methylpyridine, 2-methoxypyridine, 2- (trifluoromethyl)pyridine, 2-phenylpyridine, 3-phenylpyridine, and 4-phenylpyridine) and watersoluble (L-phenylalanine, L-tyrosine, and L-histidine) substrates. Monometallic PdNPs were active in dearomatization reactions over pyridine and its derivatives, as well as with 2- phenylpyridine and its isomers. Moreover, we found an unexpected inverse kinetic isotope effect in 2-phenylpyridine dearomatization reaction, with better results using D2 compared to H2 when Pd@NHC NPs were used as nanocatalysts. A higher difference was found with NHC-stabilized PdNPs compared to their analogues stabilized by polyvinylpyrrolidone. It suggests that NHC ligands could promote this effect based on the DFT calculations performed. In regard with watersoluble systems, bimetallic PdNiNPs were able to deuterate selectively the b position to the amino acid moiety when L-phenylalanine was used as a substrate. In this case, the aromatic reduction side process was fully suppressed thanks to a synergetic effect of both metals. On the other hand, a change in the deuteration selectivity was achieved when L-tyrosine was used as a substrate. At lower temperatures the b position to the amino acid moiety was deuterated, while at higher temperatures the deuteration took place at the ortho position with respect to the phenol group.Los compuestos deuterados han despertado gran interés en los últimos años debido a sus diversas aplicaciones. Por ejemplo, pueden utilizarse en estudios mecanísticos, para alterar perfiles farmacocinéticos y como patrones internos en diferentes técnicas acopladas a espectrometría de masas. Entre los diferentes métodos reportados para la obtención de estas moléculas, podemos destacar dos: las reacciones de Intercambio Isotópico de Hidrógeno (HIE) y las reacciones de dearomatización utilizando D2 como agente reductor. Estos procesos pueden catalizarse utilizando metales de transición tanto de forma homogénea como heterogénea. En este sentido, las nanopartículas metálicas (MNPs) han aparecido como una nueva alternativa en catálisis, especialmente en la activación de enlaces H–H y C–H, debido a sus grandes ventajas en comparación con los metales en su conformación bulk. Así pues, los ligandos Carbeno NHeterocíclicos (NHC) han desempeñado un papel importante como estabilizadores de MNPs debido a sus propiedades estereoelectrónicas únicas y versátiles, y a su capacidad para formar enlaces robustos con metales. En esta línea, se han publicado pocos reportes sobre las MNPs estabilizadas con NHC para las reacciones de deuteración, en las que se emplearon como nanocatalizadores monometálicos nanopartículas de Ru, Ir y Ni, y bimetálicos de RuIr y RuPt utilizando diferentes sustratos lipofílicos e hidrosolubles (aminoácidos). La selectividad de estos catalizadores en la deuteración principalmente es hacia posiciones cercanas a heteroátomos como el nitrógeno. Sin embargo, la reducción de los anillos aromáticos sigue siendo un gran inconveniente en las reacciones de intercambio H/D, especialmente cuando se utilizan moléculas bioactivas como los aminoácidos. En este trabajo se presenta la síntesis de nanopartículas monométiclas de Pd, Ni y bimetálicas de PdNi estabilizadas por ligandos NHC liposolubles e hidrosolubles. Las nanopartículas obtenidas se caracterizaron mediante las técnicas más avanzadas, como la microscopía electrónica de transmisión (MET), MET de alta resolución acoplado a espectroscopia de rayos X de energía dispersiva, espectroscopia infrarroja de reflectancia total atenuada, resonancia magnética nuclear en estado sólido y espectroscopia fotoelectrónica de rayos X. Se observó que estas MNP se dispersaban en medios orgánicos y acuosos debido a la estabilización y coordinación de los ligandos NHC a la superficie, con tamaños entre 1,8 y 2,9 nm.. Se probaron en reacciones de dearomatización y HIE sobre diferentes sustratos lipofílicos (piridina, 2- metilpiridina, 2-metoxipiridina, 2-(trifluorometil)piridina, 2-fenilpiridina, 3-fenilpiridina y 4- fenilpiridina) e hidrosolubles (L-fenilalanina, L-tirosina y L-histidina). Las PdNPs fueron activas en reacciones de dearomatización sobre piridina y sus derivados, así como con 2-fenilpiridina y sus isómeros. Además, se encontró un inesperado efecto cinético isotópico inverso en la reacción de dearomatización de la 2-fenilpiridina, con mejores resultados utilizando D2 en comparación con H2 cuando se utilizaron Pd@NHC NPs como nanocatalizadores, con una mayor diferencia para Pd@NHC NPs comparado con las PdNPs estabilizadas por polivinilpirrolidona. Esto sugiere que los ligandos NHC podrían promover este efecto basándose en los cálculos DFT realizados. Con respecto a los sistemas solubles en agua, las PdNiNPs fueron capaces de deuterar selectivamente la posición b a la fracción aminoácida cuando se utilizó L-fenilalanina como sustrato, evitando la reducción del anillo aromático, gracias a un efecto sinérgico de ambos metales. Por otro lado, se observó un cambio en la selectividad de la deuteración cuando se utilizó L-tirosina como sustrato. A temperaturas más bajas se deuteró la posición b con respecto a la fracción aminoácida, mientras que a temperaturas más altas la deuteración tuvo lugar en la posición orto con respecto al grupo fenol. (Texto tomado de la fuente)MaestríaMagíster en Ciencias - QuímicaNanocatálisis y Química Organometálica135 páginasapplication/pdfeng540 - Química y ciencias afinesPaladioNíquelNanopartículasIntercambio Isotópico de HidrógenoDearomatizaciónEfecto Cinético Isotópico InversoLigandos Carbeno N-HeterocíclicoPalladiumNickelNanoparticlesHydrogen Isotope ExchangeDearomatizationInverse Kinetic Isotope EffectN-Heterocyclic Carbene LigandsPd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2Nanopartículas basadas en paladio estabilizadas por ligandos carbeno NHeterocíclico: Aplicación catalítica en la transformación de moléculas nitrogenadas con D2Trabajo de grado - Maestríainfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/acceptedVersionTexthttp://purl.org/redcol/resource_type/TMBogotá - Ciencias - Maestría en Ciencias - QuímicaFacultad de CienciasBogotá, ColombiaUniversidad Nacional de Colombia - Sede BogotáGómez-Gallego, M.; Sierra, M. 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Heterocycles 2020, 101 (1), 357. https://doi.org/10.3987/COM-19-S(F)28.NanoX Graduate School of Research scholarshipProyecto código HERMES 56495EstudiantesInvestigadoresORIGINAL1032493037.2022.pdf1032493037.2022.pdfTesis de Maestría en Químicaapplication/pdf32527507https://repositorio.unal.edu.co/bitstream/unal/84336/2/1032493037.2022.pdf01df59f67fc693d0ea8464b784f1e000MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-85879https://repositorio.unal.edu.co/bitstream/unal/84336/1/license.txteb34b1cf90b7e1103fc9dfd26be24b4aMD51THUMBNAIL1032493037.2022.pdf.jpg1032493037.2022.pdf.jpgGenerated Thumbnailimage/jpeg5254https://repositorio.unal.edu.co/bitstream/unal/84336/3/1032493037.2022.pdf.jpg3790c859df89217bab2cdb5c5fa44c5dMD53unal/84336oai:repositorio.unal.edu.co:unal/843362023-08-12 23:04:01.002Repositorio Institucional Universidad Nacional de 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Pd-based nanoparticles stabilized by N-Heterocyclic carbene ligands: Application in the catalytic transformation of N-containing molecules with D2

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