TY - JOUR
T1 - Mechanism of Dinitrogen Photoactivation by P2PPhFe Complexes
T2 - Thermodynamic and Kinetic Computational Studies
AU - Prada, Camilo
AU - Dzib, Eugenia
AU - Núñez-Zarur, Francisco
AU - Salvador, Pedro
AU - Merino, Gabriel
AU - Calzado, Carmen J.
AU - Zapata-Rivera, Jhon
N1 - Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
PY - 2024/11/4
Y1 - 2024/11/4
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85207353248&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.4c04006
DO - 10.1021/acs.inorgchem.4c04006
M3 - Artículo
C2 - 39442084
AN - SCOPUS:85207353248
SN - 0020-1669
VL - 63
SP - 21364
EP - 21374
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 44
ER -