Unveiling Stereo‐Electronic Effects in Homogeneous Catalysis Integrating Theory and Experiments: the Potential of Dimeric Iron(III) Salen Complexes in Methyl Levulinate Transesterification

Abstract

Biomass represents an abundant and renewable source of raw materials that can be effectively converted into intermediates and base chemicals. Among these, levulinic acid has garnered significant attention due to its direct derivation from lignocellulosic biomass and the presence of two functional groups, a carboxylic acid, and a ketone, enabling diverse transformations into valuable products. Levulinic acid esters have already found applications in various industrial sectors such as cosmetics, plasticizers, and solvents. In this study, a broad array of alkyl levulinates has been successfully synthesized through homogeneous transesterification catalyzed by Lewis acids. A systematic screening of a library of μ‐oxo‐dinuclear Fe(III) salen complexes has been conducted, aiming to elucidate the impact of steric and electronic properties of their substituents. A complementary theoretical‐computational study based on quantum mechanics calculations and machine learning regression techniques has been employed to unravel the relationship between the structure of the catalysts and their corresponding properties, shedding light on the key factors influencing their catalytic performance.

Photophysics of a nucleic acid–protein crosslinking model strongly depends on solvation dynamics: an experimental and theoretical study

“…Using DFT potentials appears in this context the method of choice because of their good compromise between cost and accuracy, for both organic/biological 33,74–86 and inorganic/materials systems. 29,87–106 The cavity radius was determined using the equilibration procedure detailed in Section 2.2. NPBCs were enforced on the cavity by the conductor-like polarizable continuum model (C-PCM) self-consistent reaction field 107–110 ( via the ONIOM/PCM-X 111–113 formalism) and a dispersion–repulsion potential W disp–rep , 30–33,39,41,64,66–68 specifically designed by some of us for flexible solvents.…”