Acid‐Base and Anion Binding Properties of Tetrafluorinated 1, 3‐Benzodiazole, 1, 2, 3‐Benzotriazole and 2, 1, 3‐Benzoselenadiazole. Issue 22 (5th October 2021)

• Record Type: Journal Article
• Authors: Parman, Elisabeth; Lõkov, Märt; Järviste, Robert; Tshepelevitsh, Sofja; Semenov, Nikolay A.; Chulanova, Elena A.; Salnikov, Georgy E.; Prima, Darya O.; Slizhov, Yuri G.; Leito, Ivo; Zibarev, Andrey V.
• Is Part Of: Chemphyschem. Volume 22:Issue 22(2021)
• Page Start: 2329
• Page End: 2335
• Publication Date: 2021-10-05
• Subjects: acid-base properties -- anion binding -- aza-heterocycles -- hole interactions -- organofluorine compounds; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.202100475
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: The influence of fluorination on the acid‐base properties and the capacity of structurally related 6–5 bicyclic compounds – 1, 3‐benzodiazole 1, 1, 2, 3‐benzotriazole 2 and 2, 1, 3‐benzoselenadiazole 3 to σ‐hole interactions, i. e . hydrogen (1 and 2 ) and chalcogen (3 ) bondings, is studied experimentally and computationally. The tetrafluorination increases the Brønsted acidity of the diazole and triazole scaffolds and the Lewis acidity of selenadiazole scaffold decreases the basicity. Increased Brønsted acidity facilitates anion binding via the formation of hydrogen bonds; particularly, tetrafluorinated derivative of 1 (compound 4 ) binds Cl − . Increased Lewis acidity of tetrafluorinated derivative of 3 (compound 10 ), however, is not enough for binding with Cl − and F − via chalcogen bonds in contrast to previously studied Te analog of 10 . It is suggested that the maximum positive values of molecular electrostatic potential at the σ‐holes, VS, max, can be a reasonable metric for design and synthesis of new anion receptors with selenadiazole‐diazole/triazole hybrids as a special target. Related chlorinated compounds are also discussed. Abstract : Increase of Brønsted acidity of 1, 3‐benzodiazole and 1, 2, 3‐benzotriazole, and Lewis acidity of 2, 1, 3‐benzoselenadiazole, upon carbocyclic polyfluorination is quantitatively characterized. Tetrafluorinated 1, 3‐benzodiazole binds the chloride via formation of hydrogen bonds. For tetrafluorinated 2, 1, 3‐benzoselenadiazole, anion binding with the chloride and fluoride via chalcogen bonds is not observed.