Anion effect on the conformational equilibrium of sulfamide and its N, N′‐diindolyl derivative: Insights on anion transportation. (6th April 2018)

• Record Type: Journal Article
• Authors: Mendonça, João G.P.; Fernandes, Sergio A.; Cormanich, Rodrigo A.; Freitas, Matheus P.
• Is Part Of: Journal of physical organic chemistry. Volume 31:Number 9(2018)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2018-04-06
• Subjects: anion carrier -- conformation analysis -- hydrogen bonding -- sulfamide; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3850
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract: The relatively high acidity of the sulfamide hydrogens suggests a potential for the development of sulfamide derivatives as novel anion receptors. The interactions of sulfamide with F −, Cl −, CH3 COO −, and H2 PO4 − anions were spectroscopically ( 1 H and 19 F NMR) and theoretically (density functional theory) analyzed, and the complexation through hydrogen bonds was confirmed by changes in the NMR signals and theoretical calculations. The replacement of 2 sulfamide hydrogens with indolyl groups yields the N, N′ ‐diindolylsulfamide (DIS, N ‐1 H ‐indol‐4‐yl‐ N′ ‐1 H ‐indol‐7‐ylsulfuric diamide), whose bond rotations allow the interaction of 4 H(N) atoms with anions. The conformational preferences ofDIS change upon the presence of anions, but they are practically insensitive to the anion type. According to the quantum theory of atoms in molecules, natural bond orbital analysis, and NMR chemical shifts, as well as to a thermodynamic cycle, the complex with fluoride is the most stable, followed by the oxoanion‐derived models. Abstract : This work describes a theoretical study for a novel potential anion carrier, N, N′ ‐diindolylsulfamide (DIS ), which was proposed based on the parent compound sulfamide. In turn, sulfamide was spectroscopically (NMR) and theoretically evaluated, thus confirming the binding strength to fluoride, chloride, and some oxoanions.