期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 884, 期 -, 页码 17-28出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2019.01.004
关键词
Alkanes; Catalysis; Complexes of copper; Functionalization of CH bonds; Metallasilsesquioxanes; Oxidation with hydrogen peroxide; Hydroxyl radicals
资金
- RUDN University Program 5-100
- RFBR [19-03-00142, 16-53-150008, 16-29-05180, 16-03-00609]
- French Embassy in Moscow, University of Montpellier, CNRS (Programme de Recherche Conjoint)
- Ministry of Education and Science of the Russian Federation [RFMEFI61917X0007]
A simple and versatile strategy of synthesis of cage metallagermaniumsesquioxanes is demonstrated for isolation of Cu-6-based phenylgermsesquioxanes 1-6. Structure of newly synthesized coppergermses-quioxanes was established by single-crystal X-ray diffraction analysis. General principle of these cages' topology implies the presence of two linear Cu-3 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. (C) 2019 Published by Elsevier B.V.
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