We report aR h-catalyzedh ydroaminomethylation reaction of terminal alkenes in glycerolt hat proceeds efficiently under mild conditions to produce the corresponding amines in relatively high selectivity towards linear amines, moderate to excellent yields by using al ow catalyst loading (1 mol %[ Rh],2mol %p hosphine) and relative low pressure (H 2 /CO, 1:1, total pressure 10 bar). This work sheds light on the importance of glycerol in enabling enamine reduction via hydrogen transfer.M oreover,e vidence for the crucial role of Rh as chemoselective catalyst in the condensation step has been obtained for the first time in the frame of the hydroaminomethylation reaction by precluding deleterious aldol condensation reactions. The hydroaminomethylation proceeds under am olecular regime;t he outcomeo f catalytically actives peciesi nto metal-based nanoparticles renderst he catalytic system inactive.
YouTube is one of the most known
and used social networks among
students in the world, and undergraduate chemistry students are no
exception. Undeniably, YouTube can offer several advantages for complementing
university lessons in an asynchronous manner. There are many chemistry
channels available on the internet; however, they are mainly too general
or run by nonprofessionals, resulting in misconceptions or inaccuracies
that lead to student confusion. In this contribution, we present CADMIO,
a peer-to-peer reviewed YouTube channel with more than 60 videos in
Spanish language, 2,550 subscribers, and 6,000 hours of accumulated
views over the first year. These videos focus on introductory and
advanced topics in inorganic chemistry. CADMIO is a powerful, versatile,
and useful didactic tool, in which each video lesson presents basic
concepts in a clear and concise way, thorough methodologies to enhance
problem-solving skills, and an important variety of exercises to help
students learning. The wonderful and outstanding response of CADMIO
on the web and in the Faculty of Chemistry encourages us to improve
the channel, and recently, it has even become a Social Service program
in Mexico. Our unique concept for revised video content, secured by
an editorial board consisting of professors at the Facultad de Quı́mica,
UNAM, make CADMIO a truthful tool for teaching and learning chemistry.
Thiolate-capped RhNPs in imidazolium-based ionic liquids were synthesized from [Rh(μ-SR)(COD)]2 dimmers under H2 pressure without external addition of ligand stabilizers, preserving thiolate integrity on the nanoparticle surface. This nanoparticulated systems showed a remarkable selectivity that led to their application in the one pot reductive N-alkylation to produce amines.
Thioether-phosphines, 1 and 2, were applied for the stabilisation of palladium nanoparticles (PdNPs) synthesised by a bottom-up methodology, using [Pd2(dba)3] as an organometallic precursor. For the phenyl containing ligand 1, small (d(mean) = 1.6 nm), well-defined and dispersed nanoparticles were obtained; however, ligand 2 involving a long alkyl chain led to agglomerates. NMR and GC-MS analyses throughout the synthesis of the nanomaterials revealed partial cleavage of ligands by C-S and C-P bond activations, and XPS spectra of the isolated nanoparticles indicated the presence of both thioether-phosphines and their fragments on the metallic surface. Reactivity studies of molecular palladium systems as well as on extended palladium surfaces pointed out that cluster entities are responsible for C-heteroatom activations, triggering structure modifications of stabilisers during the synthesis of PdNPs.
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