RT Journal Article
T1 Infrared spectroscopy of isolated acetylacetone ion complexes with H+, Li+, and NH4+ : a tale of two tautomers
A1 Martínez-Haya, Bruno
A1 Avilés-Moreno, Juan Ramón
A1 Gámez, Francisco
A1 Martens, Jonathan
A1 Berden, Giel
A1 Oomens, Jos
K1 Acetylacetone tautomers
K1 Protonation
K1 Ion complexes
K1 Infrared ion spectroscopy
AB Acetylacetone (ACAC) is a prototypical 𝛽-diketone whose delicate keto-enol tautomeric equilibrium is highly sensitive to the interaction with external agents. In this work, we employ infrared ion spectroscopy to characterize cationic complexes of acetylacetone with H+, Li+, and NH4+, generated via electrospray ionization of methanol solution and isolated in an ion trap at room temperature. The recorded spectral signatures reveal that protonated acetylacetone is stabilized in both the enol and keto tautomeric forms of ACAC. In contrast, the complexes with Li+, and NH4+ are observed in the keto form exclusively, highlighting the decisive role of the cation in steering tautomeric preference. 𝐴𝑏 𝑖𝑛𝑖𝑡𝑖𝑜 molecular dynamics simulations expose the fluxional behavior of the protonated and ammonium-complexed species, capturing dynamical effects that static calculations fail to reproduce. These findings provide insights into cation-dependent tautomer stabilization of acetylacetone, with implications for the rationalization of the coordination chemistry of diketones in complex environments.
PB Elsevier
YR 2026
FD 2026-04-23
LK https://hdl.handle.net/10433/26532
UL https://hdl.handle.net/10433/26532
LA en
NO Journal of Molecular Spectroscopy 418–419 (2026) 112086
NO Universidad Pablo de Olavide. Departamento de Sistemas Físicos, Químicos y Naturales
DS RIO
RD May 23, 2026