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Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes: Synthesis, Structures, and Catalytic Activity in Oxidations with Peroxides
62
Citations
47
References
2017
Year
Three types of unusual cagelike copper(II) methylsilsesquioxanes, namely, nona- [(MeSiO<sub>1.5</sub>)<sub>18</sub>(CuO)<sub>9</sub>] 1, hexa- [(MeSiO<sub>1.5</sub>)<sub>10</sub>(HO<sub>0.5</sub>)<sub>2</sub>(CuO)<sub>6</sub>(C<sub>12</sub>H<sub>8</sub>N<sub>2</sub>)<sub>2</sub>(MeSiO<sub>1.5</sub>)<sub>10</sub>(HO<sub>0.5</sub>)<sub>1.33</sub>(CH<sub>3</sub>COO<sub>0.5</sub>)<sub>0.67</sub>(CuO)<sub>6</sub>(C<sub>12</sub>H<sub>8</sub>N<sub>2</sub>)<sub>2</sub>] 2, [(MeSiO<sub>1.5</sub>)<sub>10</sub>(CuO)<sub>6</sub>(MeO<sub>0.5</sub>)<sub>2</sub>(C<sub>10</sub>H<sub>8</sub>N<sub>2</sub>)<sub>2</sub>] 3, and trinuclear [(MeSiO<sub>1.5</sub>)<sub>8</sub>(CuO)<sub>3</sub>(C<sub>10</sub>H<sub>8</sub>N<sub>2</sub>)<sub>2</sub>] 4, were obtained in 44%, 27%, 20%, and 16% yields, respectively. Nuclearity and structural fashion of products was controlled by the choice of solvent system and ligand, specifically assisting the assembling of cage. Structures of 1-4 were determined by single-crystal X-ray diffraction analysis. Compounds 1 and 4 are the first cage metallasilsesquioxanes, containing nine and three Cu ions, respectively. Product 1 is the first observation of nonanuclear metallasilsesquioxane ever. Unique architecture of 4 represents early unknown type of molecular geometry, based on two condensed pentamembered siloxane cycles. Topological analysis of metal clusters in products 1-4 is provided. Complex 1 efficiently catalyzes oxidation of alcohols with tert-butylhydroperoxide TBHP to ketones or alkanes with H<sub>2</sub>O<sub>2</sub> to alkyl hydroperoxides in acetonitrile.
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