Bifurcated Chalcogen Bonds Based on One σ-Hole

Saber Mehrparvar; Christoph Wölper; Rolf Gleiter; Gebhard Haberhauer

doi:10.1055/a-1883-6076

Organic Materials, Table of Contents

CC BY-NC-ND 4.0 · Organic Materials 2022; 4(03): 43-52
DOI: 10.1055/a-1883-6076

Supramolecular Chemistry

Original Article

Bifurcated Chalcogen Bonds Based on One σ-Hole

Saber Mehrparvar

^aInstitut für Organische Chemie, Universität Duisburg-Essen, Universitätsstr. 7, 45117 Essen, Germany

,

Christoph Wölper

^aInstitut für Organische Chemie, Universität Duisburg-Essen, Universitätsstr. 7, 45117 Essen, Germany

,

Rolf Gleiter

^bOrganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany

,

Gebhard Haberhauer

^aInstitut für Organische Chemie, Universität Duisburg-Essen, Universitätsstr. 7, 45117 Essen, Germany

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Abstract

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Abstract

Chalcogen bonds are noncovalent interactions and are increasingly coming into focus for the design of complex structures in research areas such as crystal engineering, molecular recognition and catalysis. Conceptionally, chalcogen bonds can be considered as interaction between one σ-hole and one Lewis base center. Herein, we analyze the interaction between bidentate chelating ligands having two nucleophilic centers with one single σ-hole of a chalcogenazole (two-lone-pair/one-σ-hole interactions). Referring to this, we show by quantum chemical calculations and X-ray studies that three bond types are possible: in the first case, a chalcogen bond is formed between the σ-hole and only one of the Lewis base centers. In the second case, a strong bond is formed by one nucleophilic center; the second center provides only a small amount of additional stabilization. In the third case, two equivalent bonds to the σ-hole are formed by both Lewis base centers. According to the calculations, the bifurcated bonds are stronger than simple chalcogen bonds and lead to a more rigid molecular arrangement in the complex.

Key words

bifurcated bonds - chelate ligands - chalcogen bonding - DFT calculations - σ-hole

Full Text

References

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Supplementary Material

Figures and tables, Cambridge Structural Database (CSD) search, computational details, Cartesian coordinates and absolute energies for all calculated compounds, crystal structure data (CCDC numbers: 2 062 726 – 2 062 730) and NMR spectra of the new compounds are included in the Supporting Information for this article.