Unexpected Formation of the Iodobismuthate Salt (C14H15S2N2)2(C9H10SN)2[Bi4I16] upon Reaction of the Unsaturated Ligand Z-PySCH2CH=CHCH2SPy with BiI3 - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Molbank Année : 2023

Unexpected Formation of the Iodobismuthate Salt (C14H15S2N2)2(C9H10SN)2[Bi4I16] upon Reaction of the Unsaturated Ligand Z-PySCH2CH=CHCH2SPy with BiI3

Résumé

The olefinic dithioether (Z)-1,4-bis(pyridin-2-ylthio)but-2-ene Z-PyS(CH2CH=CHCH2)SPy (L) was prepared by the treatment of cis-ClCH2CH=CHCH2Cl with in situ generated potassium pyridine-2-thiolate Py-SK and analyzed by IR and NMR spectroscopy. To investigate the chemistry of polynuclear iodobismuthate complexes, two equivalents of BiI3 were reacted with L in the MeOH solution to afford the anionic tetranuclear title compound (C14H15S2N2)2(C9H10SN)2[Bi4I116] with a N-protonated (Z)-1,4-bis(pyridin-2-ylthio)but-2-ene as a counterion. Compound 1 was characterized by IR and UV spectroscopy; the formation of a tetranuclear framework was ascertained by a single-crystal X-ray diffraction study performed at 100 K. Furthermore, an unusual Bi(III)-meditated cyclization of one Z-PyS(CH2CH=CHCH2)SPy ligand occurred, affording the bicyclic pyridinium salt 3-vinyl-2,3-dihydrothiazolo[3,2-a]pyridinium bearing a terminal vinyl group, compensating the second negative charge of the Bi4I164− cluster anion. The SCXRD characterization was completed by a Hirshfeld surface analysis, revealing some secondary interactions occurring in the crystal.

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Chimie
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Dates et versions

hal-04410596 , version 1 (22-01-2024)

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Marwa Essid, Chakib Hrizi, Salah Ammar, Abderrahim Khatyr, Michael Knorr, et al.. Unexpected Formation of the Iodobismuthate Salt (C14H15S2N2)2(C9H10SN)2[Bi4I16] upon Reaction of the Unsaturated Ligand Z-PySCH2CH=CHCH2SPy with BiI3. Molbank, 2023, 2024 (1), pp.M1755. ⟨10.3390/M1755⟩. ⟨hal-04410596⟩
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