Clathrochelate iron(II) tris-nioximates with non-equivalent capping groups and their precursors: synthetic strategies, X-ray structure, and reactivity

Zelinskii, G.E.; Belov, A.S.; Chuprin, A.S.; Pavlov, A.A.; Vologzhanina, A.V.; Lebed, E.G.; Bugaenko, M.G.; Voloshin, Y.Z.

Авторы: Zelinskii Genrikh E., Belov Alexander S., Chuprin Alexander S., Pavlov Alexander A., Vologzhanina Anna V., Lebed Ekaterina G., Bugaenko Margarita G., Voloshin Yan Z.
Журнал: Journal of Coordination Chemistry
Том: 70
Номер: 13
Год издания: 2017
Издательство: Gordon and Breach Science Publishers
Местоположение издательства: Switzerland
Первая страница: 2313
Последняя страница: 2333
DOI: 10.1080/00958972.2017.1348602
Аннотация: ABSTRACT Template cross-linking of nioxime using equimolar amounts of boric and 4-vinylphenylboronic acids on an iron(II) ion as a matrix gave a mixture of mono- and divinyl-terminated clathrochelate products, which were chromatographically isolated in moderate yields and characterized by X-ray diffraction. The target complex FeNx3(BOCH3) (4-BC6H4CH=CH2) with non-equivalent capping groups was also obtained in a low yield using a transmetallation (re-boronation) of its dimethoxyboron-capped clathrochelate precursor. Re-boronation of the monomethoxyboron-capped cage complex with benzene-1,4- diboronic acid as a bifunctional Lewis-acidic agent afforded mainly the clathrochelate product of its 1:1 re-boronation having a terminal B(OH)2 group. The iron(II) clathrochelate with labile triethylantimony capping groups underwent a transmetallation on the surface of silica gel giving an immobilized Sb, Si-capped macrobicyclic intermediate. Its desorption with 4-vinylphenylboronic acid unexpectedly gave the monovinyl-terminated iron(II) semiclathrochelate as the major product, isolated in a high yield; it was X-ray structurally characterized. The geometry of FeN6-coordination polyhedra of the above semiand clathrochelates is intermediate between a trigonal prism and a trigonal antiprism; that of the monocapped iron(II) semiclathrochelate is more TAP-distorted and its pseudoencapsulated iron(II) ion is shifted from the center of this polyhedron by 0.02 Å in the direction of the capping boron atom.
Добавил в систему: Белов Александр Сергеевич

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Clathrochelate iron(II) tris-nioximates with non-equivalent capping groups and their precursors: synthetic strategies, X-ray structure, and reactivityстатья

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