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

Camilo Prada, Eugenia Dzib, Francisco Núñez-Zarur, Pedro Salvador, Gabriel Merino, Carmen J. Calzado, Jhon Zapata-Rivera

Research output: Contribution to journalArticlepeer-review

Abstract

The 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.

Original languageEnglish
Pages (from-to)21364-21374
Number of pages11
JournalInorganic Chemistry
Volume63
Issue number44
DOIs
StatePublished - 4 Nov 2024

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