High-Cluster (Cu9) Cage Silsesquioxanes: Synthesis, Structure, and Catalytic Activity

Unusual high-cluster (Cu9) cage phenylsilsesquioxanes were obtained via complexation of in situ CuII,Na-silsesquioxane species formed with phenanthroline and neocuproine. In the first case, phenanthroline, acting as "a silent ligand" (not participating in the composition of the final product), favors the formation of an unprecedented cagelike phenylsilsesquioxane of Cu9Na6 nuclearity, 1. In the second case, neocuproine ligands withdraws two Cu ions from the metallasilsesquioxane matrix, producing two cationic fragments Cu+(neocuproine)2. The remaining metallasilsesquioxane is rearranged into an anionic cage of Cu9Na4 nuclearity, finalizing the formation of a specific ionic complex, 2. The impressive molecular architecture of both types of complexes, e.g., the presence of different (cyclic/acyclic) types of silsesquioxane ligands, was established by single-crystal X-ray diffraction studies. Compound 1 was revealed to be highly active in the oxidative amidation of benzylic alcohol and the catalyst loading could be reduced down to 100 ppm of Cu. Catalytic studies of compound 1 demonstrated its high activity in hydroperoxidation of alkanes with H2O2 and oxidation of alcohols to ketones with tert-BuOOH. © 2018 American Chemical Society.

Astakhov G.S. 1, 2 , Bilyachenko A.N. 1, 2 , Korlyukov A.A.1, 3 , Levitsky M.M.1 , Shul'Pina L.S.1 , Bantreil X.4 , Lamaty F.4 , Vologzhanina A.V.1 , Shubina E.S.1 , Dorovatovskii P.V.5 , Nesterov D.S.6 , Pombeiro A.J.L.6 , Shul'Pin G.B.7, 8
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  • 1 Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Strasse 28, Moscow, Russian Federation
  • 2 Peoples' Friendship University of Russia, RUDN University, Miklukho-Maklay Strasse 6, Moscow, Russian Federation
  • 3 Pirogov Russian National Research Medical University, Ostrovitianov Strasse 1, Moscow, Russian Federation
  • 4 Institut des Biomolécules Max Mousseron, UMR 5247, CNRS, Université de Montpellier, ENSCM, Site Triolet, Place Eugène Bataillon, Montpellier cedex 5, 34095, France
  • 5 National Research Center, Kurchatov Institute, Akademika Kurchatova Place 1, Moscow, Russian Federation
  • 6 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, Lisboa, 1049-001, Portugal
  • 7 Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina, dom 4, Moscow, 119991, Russian Federation
  • 8 Plekhanov Russian University of Economics, Stremyannyi Pereulok, dom 36, Moscow, 117997, Russian Federation
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