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Multistep synthesis and X-ray structure of the carboxyl-terminated hybrid iron(II) phthalocyaninatoclathrochelates and their postsynthetic transformation into polytopic carboranyl-containing derivativesстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Chuprin Alexander S., Pavlov Alexander A., Vologzhanina Anna V., Dorovatovskii Pavel, Makarenkov Anton V., Ol'shevskaya Valentina A., Dudkin Semyon V., Voloshin Yan Z.
- Журнал: Dalton Transactions
- Том: 52
- Номер: 12
- Год издания: 2023
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 3884
- Последняя страница: 3895
- DOI: 10.1039/d3dt00076a
- Аннотация: A multistep general synthetic strategy towards the polytopic carboranyl-containing (semi)clathrochelate metal complexes, based on the template synthesis, transmetallation, amide condensation and 1,3-dipolar cycloaddition reactions, is developed. Their mono(semi)clathrochelate precursors with a single reactive group were obtained using a transmetallation of the triethylantimony-capped macrobicyclic precursor. Thus obtained carboxyl-terminated iron(II) semiclathrochelate underwent a macrobicyclization with zirconium(IV) phthalocyaninate to form the corresponding phthalocyaninatoclathrochelate. The direct one-pot template condensation of the suitable chelating and cross-linking ligand synthons on Fe2+ ion as a matrix was also used for its preparation. Further amide condensation of the aforementioned semiclathrochelate and hybrid complexes with propargylamine in the presence of carbonyldiimidazole gave the (pseudo)cage derivatives with terminal C≡C bond. Their “click” reaction with an appropriate carboranylmethyl azide afforded the ditopic carboranosemiclathrochelates and the tritopic carboranyl-containing phthalocyaninatoclathrochelates with a flexible spacer fragment between their polyhedral entities. The obtained new complexes were characterized using elemental analysis, MALDI-TOF mass spectrometry, multinuclear NMR, and UV-vis spectra, and by the single crystal X-ray diffraction experiments. Their FeN6-coordination polyhedra possess a truncated trigonal-pyramidal geometry, while the cross-linking heptacoordinate Zr4+ or Hf4+ cations in the hybrid compounds form the MIVN4O3-coordination polyhedra with the geometry of a capped trigonal prism.
- Добавил в систему: Дудкин Семён Валентинович
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