Si10Cu6N4 Cage Hexacoppersilsesquioxanes Containing N Ligands: Synthesis, Structure, and High Catalytic Activity in Peroxide Oxidations | Sciact - CRIS-system of Boreskov Institute of Catalysis

Si10Cu6N4 Cage Hexacoppersilsesquioxanes Containing N Ligands: Synthesis, Structure, and High Catalytic Activity in Peroxide Oxidations Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2017, Volume: 56, Number: 24, Pages: 15026-15040 Pages count : 15 DOI: 10.1021/acs.inorgchem.7b02320

Tags

HYDROCARBON OXYGENATIONS; SILSESQUIOXANE COMPLEXES; OLEFIN POLYMERIZATION; TETRASIL; OXIDE LIGANDS; TRANSITION-METALS; ALKANE OXIDATION; PRIMARY ALCOHOLS; BENZYL ALCOHOLS; AMIDATION; METALLASILSESQUIOXANES

Authors

Kulakova Alena N. ^1,2 , Bilyachenko Alexey N. ^1,2 , Levitsky Mikhail M. ¹ , Khrustalev Victor N. ² , Korlyukov Alexander A. ^1,3 , Zubavichus Yan V. ⁴ , Dorovatovskii Pavel V. ⁴ , Lamaty Frédéric ⁵ , Bantreil Xavier ⁵ , Villemejeanne Benoît ⁵ , Martinez Jean ⁵ , Shul’pina Lidia S. ¹ , Shubina Elena S. ¹ , Gutsul Evgeniy I. ¹ , Mikhailov Igor A. ⁶ , Ikonnikov Nikolay S. ¹ , Tsareva Ul’yana S. ¹ , Shul’pin Georgiy B. ^6,7

Affiliations

1	Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences
2	Peoples’ Friendship University of Russia (RUDN University)
3	Pirogov Russian National Research Medical University
4	National Research Center “Kurchatov Institute”
5	Institut des Biomolecules Max Mousseron (IBMM)
6	Plekhanov Russian University of Economics
7	Semenov Institute of Chemical Physics

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 Cu3 trimers is coordinated by two cyclic [PhSiO1.5]5 siloxanolate 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 9 and 14) anions. Complexes 1 and 10 exhibited a high activity in the oxidative amidation oxidation of alcohols. Compounds 1, 10, and 15 are very efficient homogeneous catalysts in the oxidation of alkanes and alcohols with peroxides.

Kulakova A.N. , Bilyachenko A.N. , Levitsky M.M. , Khrustalev V.N. , Korlyukov A.A. , Zubavichus Y.V. , Dorovatovskii P.V. , Lamaty F. , Bantreil X. , Villemejeanne B. , Martinez J. , Shul’pina L.S. , Shubina E.S. , Gutsul E.I. , Mikhailov I.A. , Ikonnikov N.S. , Tsareva U.S. , Shul’pin G.B.
Si10Cu6N4 Cage Hexacoppersilsesquioxanes Containing N Ligands: Synthesis, Structure, and High Catalytic Activity in Peroxide Oxidations

Inorganic Chemistry. 2017. V.56. N24. P.15026-15040. DOI: 10.1021/acs.inorgchem.7b02320 WOS Scopus РИНЦ ANCAN OpenAlex

Full text from publisher

Submitted:	Sep 13, 2017
Published online:	Nov 29, 2017
Published print:	Dec 18, 2017

Web of science:	WOS:000418629500036
Scopus:	2-s2.0-85038607891
Elibrary:	35525727
Chemical Abstracts:	2017:1877913
Chemical Abstracts (print):	168:83662
OpenAlex:	W2768251786

DB	Citing
Web of science	36
Scopus	36
OpenAlex	38