Chemical design of the heterodifunctionalized iron(II) clathrochelates with terminal biorelevant carboxyl group and reactive triple C≡C bond: Synthesis, structure, redox properties and their stability in various media

Selin RA, Chornenka NV, Chernii VY, Mokhir A, Vologzhanina AV, Belov AS, Pomadchik AL, Voloshin YZ (2019)


Publication Type: Journal article

Publication year: 2019

Journal

Book Volume: 496

Article Number: 119047

DOI: 10.1016/j.ica.2019.119047

Abstract

The heterodifunctionalized iron(II) clathrochelates, the molecules of which contain the terminal biorelevant carboxyl and reactive triple C≡C groups were obtained using the two-step synthetic procedures by a subsequent substitution of their dichloroclathrochelate precursor with para-carboxyphenylthiolate anion and 2-propargylamine. The complexes obtained were characterized using elemental analysis, HR-APPI and MALDI-TOF mass spectrometries, UV–Vis, 1H, 13C{1H}, 11B and 19F NMR spectroscopies, and by the single crystal X-ray diffraction for an iron(II) monochloroclathrochelate with terminal propargylamine group. Its FeN6-coordination polyhedron possesses a distorted trigonal prismatic – trigonal-antiprismatic geometry with the average distortion angle φ of approximately 26.1°. Fe–N distances in this monoribbed-functionalized molecule vary in a narrow range from 1.883(3) to 1.901(4) Å and the height h of the above polyhedron is equal to 2.30 Å. Cyclic voltammograms study of these complexes contain the single cathodic wave assigned to the metal-centered processes of the cathodic Fe2+/+ reduction and anodic Fe+/2+ re-oxidation, thus suggesting their quasi-reversible character. Chemical reactions (including a complete decomposition and a reductive hydrodehalogenation of the macrobicyclic molecules) of the propargylamine and propargylamide iron(II) clathrochelates was studied in various media and under the different experimental conditions using TLC, high-resolution APPI mass, NMR and UV–vis spectra, suggesting a complete slow destruction of the macrobicyclic frameworks of their molecules in aqueous solutions (including those modeling the physiological conditions).

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APA:

Selin, R.A., Chornenka, N.V., Chernii, V.Y., Mokhir, A., Vologzhanina, A.V., Belov, A.S.,... Voloshin, Y.Z. (2019). Chemical design of the heterodifunctionalized iron(II) clathrochelates with terminal biorelevant carboxyl group and reactive triple C≡C bond: Synthesis, structure, redox properties and their stability in various media. Inorganica Chimica Acta, 496. https://dx.doi.org/10.1016/j.ica.2019.119047

MLA:

Selin, Roman A., et al. "Chemical design of the heterodifunctionalized iron(II) clathrochelates with terminal biorelevant carboxyl group and reactive triple C≡C bond: Synthesis, structure, redox properties and their stability in various media." Inorganica Chimica Acta 496 (2019).

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