Issue 53, 2016

A heterometallic (Fe6Na8) cage-like silsesquioxane: synthesis, structure, spin glass behavior and high catalytic activity

Abstract

The exotic “Asian Lantern” heterometallic cage silsesquioxane [(PhSiO1.5)20(FeO1.5)6(NaO0.5)8(n-BuOH)9.6(C7H8)] (I) was obtained and characterized by X-ray diffraction, EXAFS, topological analyses and DFT calculation. The magnetic property investigations revealed that it shows an unusual spin glass-like behavior induced by a particular triangular arrangement of Fe(III) ions. Cyclohexane and other alkanes as well as benzene can be oxidized to the corresponding alkyl hydroperoxides and phenol, respectively, by hydrogen peroxide in air in the presence of catalytic amounts of complex I and nitric acid. The I-catalyzed reaction of cyclohexane, c-C6H12, with H216O2 in an atmosphere of 18O2 gave a mixture of labeled and non-labeled cyclohexyl hydroperoxides, c-C6H1116O–16OH and c-C6H1118O–18OH, respectively, with an 18O incorporation level of ca. 12%. Compound I also revealed high efficiency in the oxidative amidation of alcohols into amides: in the presence of complex I, only 500 ppm of iron was allowed to reach TON and TOF values of 1660 and 92 h−1.

Graphical abstract: A heterometallic (Fe6Na8) cage-like silsesquioxane: synthesis, structure, spin glass behavior and high catalytic activity

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
17 Mar 2016
Accepted
05 May 2016
First published
06 May 2016

RSC Adv., 2016,6, 48165-48180

A heterometallic (Fe6Na8) cage-like silsesquioxane: synthesis, structure, spin glass behavior and high catalytic activity

A. N. Bilyachenko, M. M. Levitsky, A. I. Yalymov, A. A. Korlyukov, A. V. Vologzhanina, Y. N. Kozlov, L. S. Shul'pina, D. S. Nesterov, A. J. L. Pombeiro, F. Lamaty, X. Bantreil, A. Fetre, D. Liu, J. Martinez, J. Long, J. Larionova, Y. Guari, A. L. Trigub, Y. V. Zubavichus, I. E. Golub, O. A. Filippov, E. S. Shubina and G. B. Shul'pin, RSC Adv., 2016, 6, 48165 DOI: 10.1039/C6RA07081G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements