期刊
CATALYSTS
卷 9, 期 9, 页码 -出版社
MDPI
DOI: 10.3390/catal9090701
关键词
alkanes; hydrogen peroxide; copper complexes; metallasilsesquioxanes
资金
- RUDN University Program 5-100
- Russian Foundation for Basic Research [19-03-142, 17-03-00993]
- Ministry of Education and Science of the Russian Federation [RFMEFI61917X0007]
- [0082-20140007]
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)(O-0(.25))(2)(phen)(3 )2. X-Ray diffraction study revealed extraordinaire molecular architectures of both products. Namely, complex 1 includes single cyclic (PhSiO1,3)(12 )silsesquioxane ligand. Four sodium ions of 1 are additionally ligated by 1,10-phenan throlines. 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 Si-6-type and (ii) unprecedented Si-7-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 pi-pi 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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