RESUMEN
The so-called dibenzyltoluene (H0-DBT) heat transfer oil contains numerous isomers of dibenzyltoluene as well as (benzyl)benzyltoluene (methyl group on the central vs. the side aromatic ring). As it is used as a liquid organic hydrogen carrier (LOHC), a detailed analysis of its composition is crucial in assessing the kinetic rate of hydrogenation for each constituent and studying the mechanism of H0-DBT hydrogenation. To identify all of the compounds in the oil, an in-depth analysis of the GC-MS spectra was performed. To confirm peak attribution, we synthesized some DBTs and characterized the pure compounds using NMR and Raman spectroscopies. Moreover, a fast-GC analysis was developed to rapidly determine the degree of hydrogenation of the mixture.
RESUMEN
We describe here a simple protocol yielding small (<2 nm) crystalline Pd2Sn nanoparticles (NPs) along with Pd homologues for sake of comparison. These NPs were obtained via an organometallic approach using Pd2(dba)3·dba (dba = dibenzylideneacetone) in THF with 2 equivalents of tributyltin hydride under 4 bars of H2 at room temperature. The Pd NP homologues were prepared similarly, using Pd2(dba)3·dba with 2 equivalents of n-octylsilane. These NPs were found to be crystalline and very small with a similar mean size (ca. 1.5 nm). These NPs were finally used as nanocatalysts in solution for a benchmark Suzuki-Miyaura cross-coupling reaction. The Pd2Sn NPs were found to be more active than Pd NPs analogues, exhibiting remarkable performances with Pd loading as low as 13 ppb. This result demonstrates a beneficial effect of tin on palladium in catalysis.
RESUMEN
This work describes the development of easy-to-prepare cobalt nanoparticles (NPs) in solution as promising alternative catalysts for alkene hydrosilylation with the industrially relevant tertiary silane 1,1,1,3,5,5,5-heptamethyltrisiloxane (MDHM). The Co NPs demonstrated high activity when used at 30 °C for 3.5-7 h in toluene, with catalyst loadings 0.05-0.2 mol %, without additives. Under these mild conditions, a set of terminal alkenes were found to react with MDHM, yielding exclusively the anti-Markovnikov product in up to 99% yields. Additionally, we demonstrated the possibility of using UV irradiation to further activate these cobalt NPs not only to enhance their catalytic performances but also to promote tandem isomerization-hydrosilylation reactions using internal alkenes, among them unsaturated fatty ester (methyl oleate), to produce linear products in up to quantitative yields.
RESUMEN
An Ir(NHC) supported catalyst is used in the selective hydrogenation of terpinen-4-ol to cis p-menthan-4-ol. Its activity, selectivity and stability are compared to those of a homogeneous homologue [IrCl(COD)MesImPr] and to a commercial Pd/C. The solid Ir catalyst is much more selective than the Pd catalyst (92 vs. 42 % at 80 °C) but also more active, more selective and more stable than the iridium complex in solution. For the first time, a supported catalyst shows an enhanced activity with respect to a complex in a diastereoselective hydrogenation reaction.
RESUMEN
A catalyst containing small (ca. 2.5 nm) and crystalline Pt nanoparticles embedded into the walls of a mesostructured silica framework was found to be highly active in alkene hydrosilylation reaching TONs of ca. 105. More importantly, no Pt leaching was detected. This result is remarkable because Pt leaching is a recurrent problem in alkene hydrosilylation, which often prevents heterogeneous catalysts from being used industrially. This result is in contrast to the significant Pt leaching observed for other Pt/SiO2 catalysts.
RESUMEN
Colloidal suspensions of monodisperse platinum nanoparticles of 2 nm diameter have been used to catalyze the hydrosilylation of 1-octene with a polymethylhydrosiloxane. The nanoparticles were found to be as efficient as Karstedt's complex, showing that colloid formation from homogeneous species during hydrosilylation reactions is not necessarily a deactivation pathway. These results also reactivated the debate on whether Karstedt's complex was truly homogeneous or colloidal during catalysis.
RESUMEN
A microstructured mesh contactor that can offer residence time of more than minutes is used for gas-liquid-solid hydrogenations and gas-liquid asymmetric hydrogenations. Applications for catalyst/chiral inductor screening and for kinetic data acquisition are demonstrated.
