Cage-like Fe,Na-Germsesquioxanes: Structure, Magnetism, and Catalytic Activity

A series of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage‐like architectures have a unique type of molecular topology consisting of the hexairon oxo {Fe6O19} core surrounded in a triangular manner by three cyclic germoxanolates [PhGe(O)O]5. This structural or...

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Published in:Angewandte Chemie International Edition 2016-12, Vol.55 (49), p.15360-15363
Main Authors: Bilyachenko, Alexey N., Levitsky, Mikhail M., Yalymov, Alexey I., Korlyukov, Alexander A., Khrustalev, Viktor N., Vologzhanina, Anna V., Shul'pina, Lidia S., Ikonnikov, Nikolay S., Trigub, Alexander E., Dorovatovskii, Pavel V., Bantreil, Xavier, Lamaty, Frédéric, Long, Jérôme, Larionova, Joulia, Golub, Igor E., Shubina, Elena S., Shul'pin, Georgiy B.
Format: Article
Language:English
Subjects:
cage compounds
homogeneous catalysis
Magnetism
metallagermsesquioxanes
oxidation
structure elucidation
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Summary:A series of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage‐like architectures have a unique type of molecular topology consisting of the hexairon oxo {Fe6O19} core surrounded in a triangular manner by three cyclic germoxanolates [PhGe(O)O]5. This structural organization induces antiferromagnetic interactions between the FeIII ions through the oxygen atoms. Evaluated for this first time in catalysis, these compounds showed a high catalytic activity in the oxidation of alkanes and the oxidative formation of benzamides from alcohols. GeOmetry: Unprecedented Fe,Na‐germsesquioxanes were synthesized. Their unique molecular topology includes a {Fe6O19} core surrounded by cyclic germoxanolates [PhGe(O)O]5. This structural organization induces antiferromagnetic interactions between FeIII ions and high catalytic activity for alkane oxidation and amide formation from benzylic alcohol and amines.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201607189