Lipidic Mesophase-Embedded Palladium Nanoparticles: Synthesis and Tunable Catalysts in Suzuki–Miyaura Cross-Coupling Reactions

M Duss, JJ Vallooran, L Salvati Manni, N Kieliger… - Langmuir, 2018 - ACS Publications
M Duss, JJ Vallooran, L Salvati Manni, N Kieliger, S Handschin, R Mezzenga, HJ Jessen
Langmuir, 2018ACS Publications
Lipidic cubic phases (LCPs) can reduce Pd2+ salts to palladium nanoparticles (PdNPs) of∼
5 nm size in their confined water channels under mild conditions. The resulting PdNP-
containing LCPs were used as nanoreactor scaffolds to catalyze Suzuki–Miyaura cross-
coupling reactions in the aqueous channels of the mesophase. To turn on catalysis, PdNP-
containing LCPs were activated by swelling the aqueous channels of the lipidic framework,
thereby enabling diffusion of the water-soluble substrates to the catalysts. The mesophases …
Lipidic cubic phases (LCPs) can reduce Pd2+ salts to palladium nanoparticles (PdNPs) of ∼5 nm size in their confined water channels under mild conditions. The resulting PdNP-containing LCPs were used as nanoreactor scaffolds to catalyze Suzuki–Miyaura cross-coupling reactions in the aqueous channels of the mesophase. To turn on catalysis, PdNP-containing LCPs were activated by swelling the aqueous channels of the lipidic framework, thereby enabling diffusion of the water-soluble substrates to the catalysts. The mesophases play a threefold role: they act as reducing agents for Pd2+, as limiting templates for their growth, and as support. The system was characterized and investigated by small-angle X-ray scattering (SAXS), cryo-transmission electron microscopy, dynamic light scattering, and nuclear magnetic resonance. Bulk LCPs and three dispersed palladium/lipid hybrid nanoparticle types were applied in the catalysis. The latter—liposomes, hexosomes, and cubosomes—can be obtained by design through combination of lipids and additives. The Suzuki–Miyaura cross-coupling of 5-iodo-2′-deoxyuridine and phenylboronic acid was used as a model reaction to study these systems. Bulk Pd-LCPs deliver the Suzuki–Miyaura product in 24 h in conversions up to 98% at room temperature, whereas with palladium/lipid dispersions at 40 °C, 68% of the starting material was transformed to the product after 72 h.
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