A heterometallic (Fe sub(6)Na sub(8)) cage-like silsesquioxane: synthesis, structure, spin glass behavior and high catalytic activity

The exotic "Asian Lantern" heterometallic cage silsesquioxane [(PhSiO sub(1.5)) sub(20)(FeO sub(1.5)) sub(6)(NaO sub(0.5)) sub(8)(n-BuOH) sub(9.6)(C sub(7)H sub(8) )] (I) was obtained and characterized by X-ray diffraction, EXAFS, topological analyses and DFT calculation. The magnetic prop...

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Bibliographic Details
Published in:RSC advances 2016-05, Vol.6 (53), p.48165-48180
Main Authors: Bilyachenko, Alexey N, Levitsky, Mikhail M, Yalymov, Alexey I, Korlyukov, Alexander A, Vologzhanina, Anna V, Kozlov, Yuriy N, Shul'pina, Lidia S, Nesterov, Dmytro S, Pombeiro, Armando JL, Lamaty, Frederic, Bantreil, Xavier, Fetre, Amandine, Liu, Diyang, Martinez, Jean, Long, Jerome, Larionova, Joulia, Guari, Yannick, Trigub, Alexander L, Zubavichus, Yan V, Golub, Igor E, Filippov, Oleg A, Shubina, Elena S, Shul'pin, Georgiy B
Format: Article
Language:English
Subjects:
Alcohols
Catalysts
Cyclohexane
Diffraction
Magnetic properties
Nitric acid
Phenol
Spin glass
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Summary:The exotic "Asian Lantern" heterometallic cage silsesquioxane [(PhSiO sub(1.5)) sub(20)(FeO sub(1.5)) sub(6)(NaO sub(0.5)) sub(8)(n-BuOH) sub(9.6)(C sub(7)H sub(8) )] (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-C sub(6)H sub(12), with H sub(2) super(16)O sub(2 ) in an atmosphere of super(18)O sub(2) gave a mixture of labeled and non-labeled cyclohexyl hydroperoxides, c-C sub(6)H sub(11)- super(16)O- super(16)OH and c-C sub(6)H sub(11)- super(18)O- super(18)OH, respectively, with an super(18)O 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 super(-1).
ISSN:2046-2069
DOI:10.1039/c6ra07081g