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Si10Cu6N4Cage Hexacoppersilsesquioxanes Containing N Ligands: Synthesis, Structure, and High Catalytic Activity in Peroxide Oxidations

Authors :
Kulakova, Alena N.
Bilyachenko, Alexey N.
Levitsky, Mikhail M.
Khrustalev, Victor N.
Korlyukov, Alexander A.
Zubavichus, Yan V.
Dorovatovskii, Pavel V.
Lamaty, Frédéric
Bantreil, Xavier
Villemejeanne, Benoît
Martinez, Jean
Shul’pina, Lidia S.
Shubina, Elena S.
Gutsul, Evgeniy I.
Mikhailov, Igor A.
Ikonnikov, Nikolay S.
Tsareva, Ul’yana S.
Shul’pin, Georgiy B.
Source :
Inorganic Chemistry; December 2017, Vol. 56 Issue: 24 p15026-15040, 15p
Publication Year :
2017

Abstract

The synthesis, composition, and catalytic properties of a new family of hexanuclear Cu(II)-based phenylsilsesquioxanes are described here. Structural studies of 17 synthesized compounds revealed the general principle underlying their molecular topology: viz., a central metal oxide layer consisting of two Cu3trimers is coordinated by two cyclic [PhSiO1.5]5siloxanolate ligands to form a skewed sandwich architecture with the composition [(PhSiO1.5)10(CuO)6]2+. In addition to this O ligation by the siloxanolate rings, two opposite copper ions are additionally coordinated by the nitrogen atoms of corresponding N ligand(s), such as 2,2′-bipyridine (compounds 1–9), 1,10-phenanthroline (compounds 10–13), mixed 1,10-phenanthroline/2,2′-bipyridine (compound 14), or bathophenanthroline (compounds 15–17). Finally, the charge balance is maintained by two HO–(compounds 1–7, 10–13, and 15–17), two H3CO–(compound 8), or two CH3COO–(compounds 9and 14) anions. Complexes 1and 10exhibited a high activity in the oxidative amidation oxidation of alcohols. Compounds 1, 10, and 15are very efficient homogeneous catalysts in the oxidation of alkanes and alcohols with peroxides.

Details

Language :
English
ISSN :
00201669 and 1520510X
Volume :
56
Issue :
24
Database :
Supplemental Index
Journal :
Inorganic Chemistry
Publication Type :
Periodical
Accession number :
ejs44069772
Full Text :
https://doi.org/10.1021/acs.inorgchem.7b02320