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

Inorganic Chemistry
Grigorii S AstakhovGeorgiy B Shul'pin

Abstract

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.

References

Oct 1, 1996·Chemical Reviews·Ramaswamy MurugavelHerbert W. Roesky
Oct 22, 2009·Inorganic Chemistry·Georgiy B Shul'pinDalmo Mandelli
Mar 17, 2010·Chemical Reviews·David B CordesFranck Rataboul
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Nov 11, 2011·Chemical Reviews·Lauren E KrenoJoseph T Hupp
Apr 6, 2013·Organic & Biomolecular Chemistry·Silvia GaspaLidia De Luca
May 8, 2015·Chemistry : a European Journal·Alexey N BilyachenkoGeorgiy B Shul'pin
May 27, 2016·Angewandte Chemie·Naoki OguriMasafumi Unno
Jun 1, 2016·Chemical Science·Maksym OpanasenkoJiří Čejka

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Citations

Mar 25, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Oksana V NesterovaDmytro S Nesterov

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