A Bidentate Antimony Pnictogen Bonding Host System

• Published in: Angewandte Chemie International Edition Vol. 62; no. 46; pp. e202310439 - n/a
• Main Authors: Beckmann, J. Louis, Krieft, Jonas, Vishnevskiy, Yury V., Neumann, Beate, Stammler, Hans‐Georg, Mitzel, Norbert W.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 13.11.2023
• Edition: International ed. in English
• Subjects: Anions; Antimony; Lewis Acid; Magnetic resonance spectroscopy; Molecular Recognition; NMR spectroscopy; Non-Covalent Interactions; Pnictogen Bond; Tin
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202310439

A bidentate pnictogen bonding host‐system based on 1,8‐diethynylanthracene was synthesized by a selective tin‐antimony exchange reaction and investigated regarding its ability to act as a Lewis acidic host component for the complexation of Lewis basic or anionic guests. In this work, the novel C≡C−Sb(C2F5)2 unit was established to study the potential of antimony(III) sites as representatives for the scarcely explored pnictogen bonding donors. The capability of this partly fluorinated host system was investigated towards halide anions (Cl−, Br−, I−), dimethyl chalcogenides Me2Y (Y=O, S, Se, Te), and nitrogen heterocycles (pyridine, pyrimidine). Insights into the adduct formation behavior as well as the bonding situation of such E⋅⋅⋅Sb−CF moieties were obtained in solution by means of NMR spectroscopy, in the solid state by X‐ray diffraction, by elemental analyses, and by computational methods (DFT, QTAIM, IQA), respectively. A bidentate pnictogen‐bonding host system based on Sb(C2F5)2 functions was constructed and its host–guest chemistry tested towards a variety of substrates including Me2O and its higher homologues, halide ions and N‐heterocyclic bases. The new host system shows cooperativity of the two C≡C−Sb(C2F5)2 functions during adduct formation. The complexes were analyzed both experimentally (XRD, NMR) and by computational methods (DFT, QTAIM, IQA).