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Formation of S-alkyl thiophenium ionic liquids: mechanistic rationale and structural relationships

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Abstract

The quaternization of thiophenes through S-alkylation reactions with iodoalkanes in the presence of silver salts opens the door to a new family of room-temperature ionic liquids, yet relatively unexplored in terms of chemical reactivity and applications. This computational study provides a mechanistic rationale that accounts for their formation. The results are consistent with the calculated energy barriers of the corresponding transition structures. Calculations indicate that the geometry at the sulfur atom goes from flat to tetrahedral during salt formation, and the electron delocalization of thiophene is greatly reduced, if not lost, as inferred from aromaticity indexes. Moreover, the rationale explains the influence of polarizable anions on S-alkylation and why alkyl substitution at the α-position of thiophenes gives rise to more stable species than unsubstituted derivatives.

Graphical abstract: Formation of S-alkyl thiophenium ionic liquids: mechanistic rationale and structural relationships

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Publication details

The article was received on 20 May 2019, accepted on 30 Jul 2019 and first published on 31 Jul 2019


Article type: Paper
DOI: 10.1039/C9OB01181A
Org. Biomol. Chem., 2019, Advance Article

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    Formation of S-alkyl thiophenium ionic liquids: mechanistic rationale and structural relationships

    M. A. Schiel, J. García de la Concepción, C. E. Domini, P. Cintas and G. F. Silbestri, Org. Biomol. Chem., 2019, Advance Article , DOI: 10.1039/C9OB01181A

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