Mechanism of Dinitrogen Photoactivation by P2PPhFe Complexes: Thermodynamic and Kinetic Computational Studies

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dc.contributor.affiliationPrada, C., Departamento de Química, Universidad de los Andes, Cra 1 No. 18A − 12, Bogotá, 111711, Colombia
dc.contributor.affiliationDzib, E., Departamento de Física Aplicada, Centro de Investigación y de Estudios Avanzados, Unidad Mérida, Km. 6 Antigua Carretera a Progreso, Apdo. Postal 73, Yucatan, Mérida, 97310, Mexico
dc.contributor.affiliationNúñez-Zarur, F., Facultad de Ciencias Básicas, Departamento de Química Física, Universidad de Medellín, Carrera 87 N° 30-65, Medellín, 050026, Colombia
dc.contributor.affiliationSalvador, P., Institut de Química Computacional i Catàlisi, Departament de Química, Universitat de Girona, Maria Aurèlia Capmany 69, Catalonia, Girona, 17003, Spain
dc.contributor.affiliationMerino, G., Departamento de Física Aplicada, Centro de Investigación y de Estudios Avanzados, Unidad Mérida, Km. 6 Antigua Carretera a Progreso, Apdo. Postal 73, Yucatan, Mérida, 97310, Mexico
dc.contributor.affiliationCalzado, C.J., Departamento de Química Física, Universidad de Sevilla, Sevilla, 41012, Spain
dc.contributor.affiliationZapata-Rivera, J., Departamento de Química, Universidad del Valle, Calle 13 N° 100−00, Cali, 760042, Colombia
dc.contributor.authorPrada C
dc.contributor.authorDzib E
dc.contributor.authorNúñez-Zarur F
dc.contributor.authorSalvador P
dc.contributor.authorMerino G
dc.contributor.authorCalzado C.J
dc.contributor.authorZapata-Rivera J.
dc.date.accessioned2025-04-28T22:09:58Z
dc.date.available2025-04-28T22:09:58Z
dc.date.issued2024
dc.descriptionThe P2PPhFe(N2)(H)2 catalyst showed a significant ammonia yield under light irradiation. However, under thermal conditions, the hydrogen evolution reaction (HER) is favored over the nitrogen reduction reaction (N2RR), making P2PPhFe(N2)(H)2 an ideal system for studying the competition between both reactions. In this study, we used a series of computational tools to elucidate the photochemical reaction mechanism for the N2RR and thermal pathways leading to the HER with this catalyst. We calculated the energy profile for each transformation and estimated the rate constants for each step. Our results, which are consistent with experimental observations, indicate that photoinduced H2 elimination from P2PPhFe(N2)(H)2 promotes the formation of P2PPhFe(N2)2, which is on-path for N2RR. However, this elimination process is kinetically hindered due to high-energy barriers. Furthermore, our calculations reveal enhanced dinitrogen activation upon the conversion of P2PPhFe(N2)(H)2 to P2PPhFe(N2)2 © 2024 The Authors. Published by American Chemical Society.
dc.identifier.doi10.1021/acs.inorgchem.4c04006
dc.identifier.instnameinstname:Universidad de Medellínspa
dc.identifier.issn201669
dc.identifier.reponamereponame:Repositorio Institucional Universidad de Medellínspa
dc.identifier.repourlrepourl:https://repository.udem.edu.co/
dc.identifier.urihttp://hdl.handle.net/11407/8863
dc.language.isoeng
dc.publisherAmerican Chemical Societyspa
dc.publisher.facultyFacultad de Ciencias Básicasspa
dc.relation.isversionofhttps://www.scopus.com/inward/record.uri?eid=2-s2.0-85207353248&doi=10.1021%2facs.inorgchem.4c04006&partnerID=40&md5=2ac95859c7036690339d5a0eb862787a
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dc.rights.accessrightsinfo:eu-repo/semantics/restrictedAccess
dc.sourceInorganic Chemistry
dc.sourceInorg. Chem.
dc.sourceScopus
dc.subjectActivation energy
dc.subjectAmmonia
dc.subjectEnergy barriers
dc.subjectPhotochemical reactions
dc.subjectSpecific energy
dc.subjectComplex kinetics
dc.subjectComplex thermodynamics
dc.subjectComputational studies
dc.subjectDinitrogen
dc.subjectFe complexes
dc.subjectHydrogen evolution reactions
dc.subjectLight irradiations
dc.subjectPhoto activations
dc.subjectThermodynamics and kinetics
dc.subject]+ catalyst
dc.subjectRate constants
dc.titleMechanism of Dinitrogen Photoactivation by P2PPhFe Complexes: Thermodynamic and Kinetic Computational Studies
dc.typeArticle
dc.type.localArtículo revisado por paresspa
dc.type.versioninfo:eu-repo/semantics/publishedVersion

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