Dendrimer-Stabilized Metal Nanoparticles as Efficient Catalysts for Reversible Dehydrogenation/Hydrogenation of N‑Heterocycles

• Published in: Journal of the American Chemical Society 2017-12, Vol.139 (49), p.18084-18092
• Main Authors: Deraedt, Christophe, Ye, Rong, Ralston, Walter T, Toste, F. Dean, Somorjai, Gabor A
• Format: Article
• Language: English
• Subjects: INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.7b10768

Nanoparticles (Pd, Pt, Rh) stabilized by G4OH PAMAM dendrimers and supported in SBA-15 (MNPs/SBA-15 with M = Pd, Pt, Rh) were efficiently used as catalysts in the acceptorless dehydrogenation of tetrahydroquinoline/indoline derivatives in toluene (release of H2) at 130 °C. These catalysts are air stable, very active, robust, and recyclable during the process. The reverse hydrogenation reaction of quinoline derivatives (H2 storage) was also optimized and successfully performed in the presence of the same catalysts in toluene at 60 °C under only 1 atm of hydrogen gas. Such catalysts may be essential for the adoption of organic hydrogen-storage materials as an alternative to petroleum-derived fuels. Hot filtration test confirmed that the reaction follows a heterogeneous pathway. Moreover, PdNPs/SBA-15 was an excellent catalyst for the direct arylation at the C-2 position (via C–H activation) of indole in water in the presense of a hypervalent iodine oxidant. Thus, a one-pot dehydrogenation/direct arylation cascade reaction between indoline and an arylated agent was efficaciously performed in water, demonstrating the potential of the system to catalyze tandem heterogeneous/homogeneous processes by choice of the appropriate oxidant/reductant.