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Multistep synthesis, reactivity and X-ray structure of the anisole-terminated iron(II) polyhalogenoclathrochelates and their monoribbed-functionalized macrobicyclic derivatives

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Abstract

Multistep synthetic pathway towards a series of the anisoleboron-capped ribbed-functionalized iron(II) cage complexes was developed. Their hexachloroclathrochelate precursor was obtained by the template condensation of three dichloroglyoximate chelating ligand synthons with two molecules of 4-methoxyphenylboronic acid as a Lewis-acidic cross-linking agent on the iron(II) ion as a matrix. It easily underwent a stepwise nucleophilic substitution with S2- and O2-dinucleophilic aliphatic (ethanedithiolate) or aromatic (pyrocatecholate) agents, forming the stable X2 (X = S or O)-six-membered ribbed substituent(s) at a quasiaromatic cage framework. Performing these reactions under the different reaction conditions (i.e., at various hexachloroclathrochelate-to-nucleophile molar ratios, a wide range of temperatures and a series of the solvents) allowed to control a predominant formation of its mono-, di- or triribbed-substituted macrobicyclic derivatives. Thus obtained iron(II) di- and tetrachloroclathrochelates can undergo their post-synthetic transformations with active nucleophilic agents. The latter complexes underwent a further nucleophilic substitution with the anionic derivative of n-butanthiol, thus giving the hexasulfide macrobicyclic compound with two functionalizing n-alkyl substituents in one of its three chelate α-dioximate fragments and two apical biorelevant anisole substituents. The obtained iron(II) clathrochelates, possessing a low-spin electronic d6 configuration, were characterized using elemental analysis, MALDI-TOF mass spectrometry, UV–Vis, 1H and 13C{1H} NMR spectroscopies, and by the single-crystal X-ray diffraction experiments for the hexachloroclathrochelate precursor, its dichlorotetrasulfide macrobicyclic derivative and the monoribbed-functionalized hexasulfide cage complex. In all their molecules, the encapsulated iron(II) ion is situated in the centre of its FeN6-coordination polyhedron, the geometry of which is intermediate between a trigonal prism and a trigonal antiprism with the distortion angles φ from 21.4 to 23.4°. Halogen bonding between the polyhalogenoclathrochelate molecules in their crystals is observed.

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Acknowledgements

The synthesis of clathrochelate complexes was supported by Russian Science Foundation (project 21-73-20145). G.E.Z. also thanks the RFBR (grant 19-33-60047) for the financial support. NMR measurements were carried out using the equipment of Center for molecular composition studies of INEOS RAS. UV-Vis measurements were supported by IGIC RAS state assignment. MALDI-TOF mass spectrometric measurements were performed using the equipment of CKP FMI IPCE RAS. The unique scientific equipment Kurchatov Synchrotron Radiation source at the NRC Kurchatov Institute was used to perform the synchrotron single-crystal XRD experiments.

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Authors and Affiliations

  1. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28–1 Vavilova st, Moscow, Russia, 119334

    Ilya P. Limarev, Genrikh E. Zelinskii, Danila O. Mosov, Anna V. Vologzhanina, Ekaterina G. Lebed & Yan Z. Voloshin

  2. Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, 31 Leninsky pr, Moscow, Russia, 119991

    Ilya P. Limarev, Genrikh E. Zelinskii, Ekaterina G. Lebed & Yan Z. Voloshin

  3. National Research Center “Kurchatov Institute”, 1 Kurchatova pl, Moscow, Russia, 123098

    Pavel V. Dorovatovskii & Vladimir A. Lazarenko

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  1. Ilya P. Limarev
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  2. Genrikh E. Zelinskii
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  3. Danila O. Mosov
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  4. Anna V. Vologzhanina
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  8. Yan Z. Voloshin
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The manuscript was written through the contributions of all authors. All authors have given approval to the final version of this manuscript. Its authors contributed equally.

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Correspondence to Yan Z. Voloshin.

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Limarev, I.P., Zelinskii, G.E., Mosov, D.O. et al. Multistep synthesis, reactivity and X-ray structure of the anisole-terminated iron(II) polyhalogenoclathrochelates and their monoribbed-functionalized macrobicyclic derivatives. Transit Met Chem 47, 321–331 (2022). https://doi.org/10.1007/s11243-022-00515-6

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