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).
Authors with CRIS profile
Involved external institutions
Vernadsky Institute of general and inorganic chemistry / Інститут загальної та неорганічної хімії імені В. I. Вернадського НАН України
Ukraine (UA)
A.N.Nesmeyanov Institute of Organoelement Compounds (INEOS RAS) / Институт элементоорганических соединений Российской Академии Наук им. А.Н. Несмеянова (ИНЭОС РАН)
Russian Federation (RU)
Ukraine (UA)
A.N.Nesmeyanov Institute of Organoelement Compounds (INEOS RAS) / Институт элементоорганических соединений Российской Академии Наук им. А.Н. Несмеянова (ИНЭОС РАН)
Russian Federation (RU)
How to cite
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://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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