Hexacoppergermsesquioxanes as Complexes with N-Ligands: Synthesis, Structure and Catalytic Properties Full article
Journal |
Journal of Organometallic Chemistry
ISSN: 0022-328X |
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Output data | Year: 2019, Volume: 884, Pages: 17-28 Pages count : 12 DOI: 10.1016/j.jorganchem.2019.01.004 | ||||||||||||||||
Tags | Alkanes; Catalysis; Complexes of copper; Functionalization of CH bonds; Metallasilsesquioxanes; Oxidation with hydrogen peroxide; Hydroxyl radicals | ||||||||||||||||
Authors |
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Affiliations |
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Funding (9)
1 | The Ministry of Education and Science of the Russian Federation | |
2 | Russian Foundation for Basic Research | 16-03-00609 (АААА-А15-115123110094-2) |
3 | Russian Foundation for Basic Research | 16-53-150008 (АААА-А16-116031110130-4) |
4 | The Ministry of Education and Science of the Russian Federation | 14.619.21.0007 (RFMEFI61917X0007)(АААА-А18-118011190114-0) |
5 | Russian Foundation for Basic Research | 19-03-00142 |
6 | Russian Foundation for Basic Research | 16-29-05180 (АААА-А16-116031110127-4) |
7 | French Embassy in Moscow | |
8 | University of Montpellier, Institute of Biomolecules Max Mousseron | |
9 | French National Centre for Scientific Research |
Abstract:
A simple and versatile strategy of synthesis of cage metallagermaniumsesquioxanes is demonstrated for isolation of Cu6-based phenylgermsesquioxanes 1–6. Structure of newly synthesized coppergermsesquioxanes was established by single-crystal X-ray diffraction analysis. General principle of these cages' topology implies the presence of two linear Cu3 fragments, coordinated by three pairs of ligands. These are: (i) cyclic germsesquioxanes [PhGeO1,5]5, products 1–6, (ii) 1,10-phenanthrolines, (1, 3–5) or 2,2’-bipyridines, (2, 6), (or and (iii) OX species (X = H, 1–2, CH3, 3, H and C2H5O, 4, HCO, 5, CH3CO, 6). Appearance of non-expected species (formiate for 5, acetate for 6), resulted from corresponding alcohols used as reaction media, points at easyness of oxidation processes in the conditions of such self-assembling reactions. Catalytic tests showed high activity of complexes 1 and 2 as precatalysts in homogeneous oxidations of alkanes (cyclohexane, methylcyclohexane, n-heptane, cis-1,2-dimethylcyclohexane with hydrogen peroxide in acetonitrile solution. Hydroxyl radicals take part in the reaction. The same complexes catalyze oxidation of alcohols (cyclohexanol, 2-heptanol, 1-phenylethanol) to corresponding ketones with tert-butyl hydroperoxide in almost 100% yield. With the addition of various alkyl ammonium salts, complex 2 could also furnish corresponding amides in high yield.
Cite:
Kulakova A.N.
, Korlyukov A.A.
, Zubavichus Y.V.
, Khrustalev V.N.
, Bantreil X.
, Shul'pina L.S.
, Levitsky M.M.
, Ikonnikov N.S.
, Shubina E.S.
, Lamaty F.
, Bilyachenko A.N.
, Shul'pin G.B.
Hexacoppergermsesquioxanes as Complexes with N-Ligands: Synthesis, Structure and Catalytic Properties
Journal of Organometallic Chemistry. 2019. V.884. P.17-28. DOI: 10.1016/j.jorganchem.2019.01.004 WOS Scopus РИНЦ РИНЦ
Hexacoppergermsesquioxanes as Complexes with N-Ligands: Synthesis, Structure and Catalytic Properties
Journal of Organometallic Chemistry. 2019. V.884. P.17-28. DOI: 10.1016/j.jorganchem.2019.01.004 WOS Scopus РИНЦ РИНЦ
Files:
Full text from publisher
Dates:
Submitted: | Nov 9, 2018 |
Accepted: | Jan 8, 2019 |
Published online: | Jan 24, 2019 |
Published print: | Mar 30, 2019 |
Identifiers:
Web of science | WOS:000458779500002 |
Scopus | 2-s2.0-85060892552 |
Elibrary | 38661182 , 41789205 |
Chemical Abstracts | 2019:241926 |
OpenAlex | W2914901589 |