Die Natur starker Chalkogenbindungen unter Beteiligung chalkogenhaltiger Heterocyclen

Haberhauer, Gebhard; Gleiter, Rolf

doi:10.1002/ange.202010309

Cited by 4 publications

(1 citation statement)

References 60 publications

(84 reference statements)

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“…Continuing research has revealed the occurrence of these bonds in biomolecules such as proteins and nucleic acids [21,35–39] or SAM riboswitches [36] . The ChB runs a full spectrum of bond strength [40] with Te being particularly strong, [41] and reveals itself in a number of ways including solid state NMR [42,43] . A good deal of our present understanding of the ChB is contained in a number of recent review articles [24,44–48] to which an interested reader is referred.…”

Section: Introductionmentioning

confidence: 99%

Competition Between the Two σ‐Holes in the Formation of a Chalcogen Bond

Scheiner

2023

ChemPhysChem

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A chalcogen atom Y contains two separate σ-holes when in a R 1 YR 2 molecular bonding pattern. Quantum chemical calculations consider competition between these two σ-holes to engage in a chalcogen bond (ChB) with a NH 3 base. R groups considered include F, Br, I, and tert-butyl (tBu). Also examined is the situation where the Y lies within a chalcogenazole ring, where its neighbors are C and N. Both electron-withdrawing substituents R 1 and R 2 act cooperatively to deepen the two σ-holes, but the deeper of the two holes consistently lies opposite to the more electron-withdrawing group, and is also favored to form a stronger ChB. The formation of two simultaneous ChBs in a triad requires the Y atom to act as double electron acceptor, and so anti-cooperativity weakens each bond relative to the simple dyad. This effect is such that some of the shallower σ-holes are unable to form a ChB at all when a base occupies the other site.

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Section: Introductionmentioning

confidence: 99%

Competition Between the Two σ‐Holes in the Formation of a Chalcogen Bond

Scheiner

2023

ChemPhysChem

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Non‐classical Non‐covalent σ‐Hole Interactions in Protein Structure and Function: Concepts for Potential Protein Engineering Applications

Walker

Mendez

2023

Chemistry An Asian Journal

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The structures and associated functions of biological molecules are driven by noncovalent interactions, which have classically been dominated by the hydrogen bond (H-bond). Introduction of the σ-hole concept to describe the anisotropic distribution of electrostatic potential of covalently bonded elements from across the periodic table has opened a broad range of nonclassical noncovalent (ncNC) interactions for applications in chemistry and biochemistry. Here, we review how halogen bonds, chalcogen bonds and tetrel bonds, as they are found naturally or introduced synthetically, affect the structures, assemblies, and potential functions of peptides and proteins. This review intentionally focuses on examples that introduce or support principles of stability, assembly and catalysis that can potentially guide the design of new functional proteins. These three types of ncNC interactions have energies that are comparable to the Hbond and, therefore, are now significant concepts in molecular recognition and design. However, the recently described H-bond enhanced X-bond shows how synergism among ncNC interactions can be exploited as potential means to broaden the range of their applications to affect protein structures and functions.

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Intermolecular Covalent Interactions: Nature and Directionality

Santos

Ramalho

Hamlin

et al. 2023

Chemistry A European J

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Quantum chemical methods were employed to analyze the nature and the origin of the directionality of pnictogen (PnB), chalcogen (ChB), and halogen bonds (XB) in archetypal FmZ⋅⋅⋅F− complexes (Z=Pn, Ch, X), using relativistic density functional theory (DFT) at ZORA‐M06/QZ4P. Quantitative Kohn‐Sham MO and energy decomposition analyses (EDA) show that all these intermolecular interactions have in common that covalence, that is, HOMO−LUMO interactions, provide a crucial contribution to the bond energy, besides electrostatic attraction. Strikingly, all these bonds are directional (i.e., F−Z⋅⋅⋅F− is approximately linear) despite, and not because of, the electrostatic interactions which, in fact, favor bending. This constitutes a breakdown of the σ‐hole model. It was shown how the σ‐hole model fails by neglecting both, the essential physics behind the electrostatic interaction and that behind the directionality of electron‐rich intermolecular interactions. Our findings are general and extend to the neutral, weaker ClI⋅⋅⋅NH3, HClTe⋅⋅⋅NH3, and H2ClSb⋅⋅⋅NH3 complexes.

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Die Natur starker Chalkogenbindungen unter Beteiligung chalkogenhaltiger Heterocyclen

Cited by 4 publications

References 60 publications

Competition Between the Two σ‐Holes in the Formation of a Chalcogen Bond

Competition Between the Two σ‐Holes in the Formation of a Chalcogen Bond

Non‐classical Non‐covalent σ‐Hole Interactions in Protein Structure and Function: Concepts for Potential Protein Engineering Applications

Intermolecular Covalent Interactions: Nature and Directionality

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