77387-57-6Relevant articles and documents
A bio-inspired imidazole-functionalised copper cage complex
Bete, Sarah C.,Würtele, Christian,Otte, Matthias
, p. 4427 - 4430 (2019)
An imidazole-functionalised cage is synthesised that can coordinate to Cu(i). X-ray analysis reveals a T-shaped coordination of copper by the imidazole ligands reminiscent of the coordination geometry found in enzymatic active sites. This cage complex can
Surface-Plasmon-Mediated Hydrogenation of Carbonyls Catalyzed by Silver Nanocubes under Visible Light
Landry, Michael J.,Gellé, Alexandra,Meng, Beryl Y.,Barrett, Christopher J.,Moores, Audrey
, p. 6128 - 6133 (2017/09/15)
Plasmonic nanoparticles are exciting and promising candidates for light-activated catalysis. We report herein the use of plasmonic nanocubes for the activation of molecular hydrogen and the hydrogenation of ketones and aldehydes via visible light irradiation at 405 nm, corresponding to the position of the plasmon band of the nanocubes, at 80 °C. Only 1 atm of molecular hydrogen is required to access, using catalytic amounts of silver, primary, and secondary alcohols, with complete chemoselectivty for C=O over C=C reduction. The resulting catalytic system was studied over a scope of 12 compounds. Exposure to other wavelengths, or absence of light failed to provide activity, thus proving a direct positive impact of the plasmonic excitation to the catalytic activity. By varying the irradiation intensity, we studied the relationship between plasmon band excitation and catalytic activity and propose a potential reaction mechanism involving plasmon-activated hot electrons. This study expands the scope of reactions catalyzed by free-standing plasmonic particles and sheds light on H2 activation by silver surfaces.
Hydrogen atom abstraction reactions from tertiary amines by benzyloxyl and cumyloxyl radicals: Influence of structure on the rate-determining formation of a hydrogen-bonded prereaction complex
Salamone, Michela,Dilabio, Gino A.,Bietti, Massimo
, p. 6264 - 6270 (2011/10/08)
A time-resolved kinetic study on the hydrogen atom abstraction reactions from a series of tertiary amines by the cumyloxyl (CumO?) and benzyloxyl (BnO?) radicals was carried out. With the sterically hindered triisobutylamine, comparable hydrogen atom abstraction rate constants (kH) were measured for the two radicals (kH(BnO ?)/kH(CumO?) = 2.8), and the reactions were described as direct hydrogen atom abstractions. With the other amines, increases in kH(BnO?)/kH(CumO ?) ratios of 13 to 2027 times were observed. kH approaches the diffusion limit in the reactions between BnO? and unhindered cyclic and bicyiclic amines, whereas a decrease in reactivity is observed with acyclic amines and with the hindered cyclic amine 1,2,2,6,6-pentamethylpiperidine. These results provide additional support to our hypothesis that the reaction proceeds through the rate-determining formation of a C-H/N hydrogen-bonded prereaction complex between the benzyloxyl α-C-H and the nitrogen lone pair wherein hydrogen atom abstraction occurs, and demonstrate the important role of amine structure on the overall reaction mechanism. Additional mechanistic information in support of this picture is obtained from the study of the reactions of the amines with a deuterated benzyloxyl radical (PhCD2O?, BnO?- d2) and the 3,5-di-tert-butylbenzyloxyl radical.
