New Cu4Na4- and Cu5-Based Phenylsilsesquioxanes. Synthesis via Complexation with 1,10-Phenanthroline, Structures and High Catalytic Activity in Alkane Oxidations with Peroxides in Acetonitrile
by
Grigorii S. Astakhov 1,2, Mikhail M. Levitsky 1, Alexander A. Korlyukov 1,3
, Lidia S. Shul’pina 1, Elena S. Shubina 1, Nikolay S. Ikonnikov 1, Anna V. Vologzhanina 1, 
Aleksey N. Bilyachenko 1,2,*, Pavel V. Dorovatovskii 4, Yuriy N. Kozlov 5,6 and Georgiy B. Shul’pin 2,5,6,*
, Lidia S. Shul’pina 1, Elena S. Shubina 1, Nikolay S. Ikonnikov 1, Anna V. Vologzhanina 1, Aleksey N. Bilyachenko 1,2,*, Pavel V. Dorovatovskii 4, Yuriy N. Kozlov 5,6 and Georgiy B. Shul’pin 2,5,6,*
1
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ulitsa Vavilova, 28, Moscow 119991, Russia
2
Peoples’ Friendship University of Russia, ulitsa Miklukho-Maklaya, 6, Moscow 117198, Russia
3
Pirogov Russian National Research Medical University, ulitsa Ostrovitianova, 1, Moscow 117997, Russia
4
National Research Center “Kurchatov Institute”, pl. Akademika Kurchatova, 1, Moscow 123098, Russia
5
Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina, 4, Moscow 119991, Russia
6
Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi pereulok, 36, Moscow 117997, Russia
*
Authors to whom correspondence should be addressed.
Catalysts 2019, 9(9), 701; https://doi.org/10.3390/catal9090701
Received: 6 August 2019 / Revised: 17 August 2019 / Accepted: 17 August 2019 / Published: 21 August 2019
(This article belongs to the Special Issue Advance in Catalytic C−H Functionalization for Chemical Synthesis and Other Applications)
Self-assembly of copper(II)phenylsilsesquioxane assisted by the use of 1,10-phenanthroline (phen) results in isolation of two unusual cage-like compounds: (PhSiO1,5)12(CuO)4(NaO0.5)4(phen)4 1 and (PhSiO1,5)6(PhSiO1,5)7(HO0.5)2(CuO)5(O0.25)2(phen)3 2. X-Ray diffraction study revealed extraordinaire molecular architectures of both products. Namely, complex 1 includes single cyclic (PhSiO1,5)12 silsesquioxane ligand. Four sodium ions of 1 are additionally ligated by 1,10-phenanthrolines. In turn, “sodium-less” complex 2 represents coordination of 1,10-phenanthrolines to copper ions. Two silsesquioxane ligands of 2 are: (i) noncondensed cubane of a rare Si6-type and (ii) unprecedented Si7-based ligand including two HOSiO1.5 fragments. These silanol units were formed due to removal of phenyl groups from silicon atoms, observed in mild conditions. The presence of phenanthroline ligands in products 1 and 2 favored the π–π stacking interactions between neighboring cages. Noticeable that in the case of 1 all four phenanthrolines participated in such supramolecular organization, unlike to complex 2 where one of the three phenanthrolines is not “supramolecularly active”. Complexes 1 and 2 were found to be very efficient precatalysts in oxidations with hydroperoxides. A new method for the determination of the participation of hydroxyl radicals has been developed.
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Keywords:
alkanes; hydrogen peroxide; copper complexes; metallasilsesquioxanes
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MDPI and ACS Style
Astakhov, G.S.; Levitsky, M.M.; Korlyukov, A.A.; Shul’pina, L.S.; Shubina, E.S.; Ikonnikov, N.S.; Vologzhanina, A.V.; Bilyachenko, A.N.; Dorovatovskii, P.V.; Kozlov, Y.N.; Shul’pin, G.B. New Cu4Na4- and Cu5-Based Phenylsilsesquioxanes. Synthesis via Complexation with 1,10-Phenanthroline, Structures and High Catalytic Activity in Alkane Oxidations with Peroxides in Acetonitrile. Catalysts 2019, 9, 701.
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