Cu42Ge24Na4—A Giant Trimetallic Sesquioxane Cage: Synthesis, Structure, and Catalytic Activity

Alena Kulakova (1) , Alexey Bilyachenko (1) , Victor N. Khrustalev (1) , Yan Zubavichus (2) , Pavel V. Dorovatovskii (2) , Lidia Shul’pina (1) , Xavier Bantreil (3) , Frédéric Lamaty (3) , Elena V Shubina (1) , Mikhail Levitsky (1) , Georgiy Shul’pin (4)

1 INEOS - A. N. Nesmeyanov Institute of Organoelement Compounds
2 NRC KI - National Research Center "Kurchatov Institute"
3 IBMM - Institut des Biomolécules Max Mousseron [Pôle Chimie Balard]
4 N. N. Semenov Institute of Chemical Physics

Unprecedented germanium-based sesquioxane exhibits an extremely high nuclearity (Cu 42 Ge 24 Na 4) and unusual encapsulation features. The compound demonstrated a high catalytic activity in the oxidative amidation of alcohols, with cost-effective catalyst loading down to 400 ppm of copper, and in the oxidation of cyclohexane and other alkanes with H 2 O 2 in acetonitrile in the presence of nitric acid. Selectivity parameters and the mode of dependence of initial cyclohexane oxidation rate on initial concentration of the hydrocarbon indicate that the reaction occurs with the participation of hydroxyl radicals and alkyl hydroperoxides are formed as the main primary product. Alcohols have been transformed into the corresponding ketones by the catalytic oxidation with tert-butyl hydroperoxide.

Mots clés: hydrogen peroxide; amides; alkanes; multinuclear complexes; iron complexes; metallasiloxanes

Domaines: Matériaux; Catalyse

Alena Kulakova, Alexey Bilyachenko, Victor N. Khrustalev, Yan Zubavichus, Pavel V. Dorovatovskii, et al.. Cu42Ge24Na4—A Giant Trimetallic Sesquioxane Cage: Synthesis, Structure, and Catalytic Activity. Catalysts, 2018, 8 (10), pp.484. ⟨10.3390/catal8100484⟩. ⟨hal-02370770⟩