Iron-Catalyzed Homogeneous Hydrosilylation of Ketones and Aldehydes: Advances and Mechanistic Perspective

ACS Catalysis 9(6): 5400-5417 (2019)This review is focused on iron-based homogeneous catalytic systems described so far for the reduction of carbonyl compounds (ketones and aldehydes) into alcohols via hydrosilylation. It begins by explaining the basic concepts of the hydrosilylation reaction, addressing its main advantages and procedural differences with other common reduction methods, and highlighting the interest for its use in organic chemistry. Then, the advances in the development of iron-based catalysts, as a more sustainable alternative to the traditional noble-metal catalysts, that have taken place to date are reviewed in depth. The revision of the different types of catalysts is followed by a profound discussion of the mechanistic proposals found in the literature.This work was supported by the Junta de Andalucı́a (project number P12-FQM-2668) and the Ministerio de Ciencia, Innovación y Universidades (project number CTQ2017-84334-R). A.R.-B. thanks University of Almerı́a for a Ph.D. fellowship and P.O.-B. thanks MEC for a Ramón y Cajal contract (RYC-2014-16620).Peer reviewe

l ‐Lysine Stabilized FeNi Nanoparticles for the Catalytic Reduction of Biomass‐Derived Substrates in Water Using Magnetic Induction

International audienceThe reduction of biomass‐derived compounds gives access to valuable chemicals from renewable sources, circumventing the use of fossil feedstocks. Herein, we describe the use of iron‐nickel magnetic nanoparticles for the reduction of biomass model compounds in aqueous media under magnetic induction. Nanoparticles with a hydrophobic ligand (FeNi 3 ‐PA, PA=palmitic acid) have been employed successfully, and their catalytic performance is intended to improve by ligand exchange with lysine (FeNi 3 ‐Lys and FeNi 3 @Ni‐Lys NPs) to enhance water dispersibility. All three catalysts have been used to hydrogenate 5‐hydroxymethylfurfural into 2,5‐bis(hydroxymethyl)furan with complete selectivity and almost quantitative yields, using 3 bar of H 2 and a magnetic field of 65 mT in water. These catalysts have been recycled up to 10 times maintaining high conversions. Under the same conditions, levulinic acid has been hydrogenated to γ‐valerolactone, and 4’‐hydroxyacetophenone hydrodeoxygenated to 4‐ethylphenol, with conversions up to 70 % using FeNi 3 ‐Lys, and selectivities above 85 % in both cases. This promising catalytic system improves biomass reduction sustainability by avoiding noble metals and expensive ligands, increasing energy efficiency via magnetic induction heating, using low H 2 pressure, and proving good reusability while working in an aqueous medium

Determination of the Surface Temperature of Magnetically Heated Nanoparticles using a Catalytic Approach

International audienceHerein we describe a new method for the determination of the surface temperature of magnetically heated nanoparticles in solution using the temperature dependency of the catalytic performances of iron carbide nanoparticles coated with ruthenium (Fe2.2C@Ru) for acetophenone hydrodeoxygenation. A correlation between nanoparticle surface temperature and magnetic field could be established. Very high surface temperatures could be estimated in different solvents, which were also found similar at a given magnetic field and well above some solvent boiling points

Induction heating: an efficient methodology for the synthesis of functional core–shell nanoparticles

International audienceWhile magnetic induction heating has found uses in hyperthermia, metallurgy, and catalysis, its potential in material synthesis remains largely unexplored. This study unveils its promising role in crafting core-shell nanoparticles from magnetic cores