σ/π-Hole noble gas bonding interactions: Insights from theory and experiment

Bauzá, Antonio

doi:10.1016/j.ccr.2019.213112

Cited by 95 publications

(83 citation statements)

References 115 publications

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“…Much progress in crystal engineering and supramolecular biochemistry involving molecular recognition and selfassembly in the recent past was spurred by use of directional noncovalent interactions like hydrogen, halogen and chalcogen bonds (Bibelayi et al, 2016;Bauzá et al, 2020). The geometric data derived from the CSD provided experimental support for -hole interactions of R 1 -S-R 2 groups, which probably play an important role in stabilizing some crystal structures.…”

Section: Discussionmentioning

confidence: 99%

σ-Hole interactions in small-molecule compounds containing divalent sulfur groupsR₁—S—R₂

Lundemba

Bibelayi

Wood

et al. 2020

Acta Crystallogr B Struct Sci Cryst Eng Mater

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Hydrogen bonds, aromatic stacking contacts and σ-hole interactions are all noncovalent interactions commonly observed in biological systems. Structural data derived from the Protein Data Bank showed that methionine residues can interact with oxygen atoms through directional S...O contacts in the protein core. In the present work, the Cambridge Structural Database (CSD) was used in conjunction with ab initio calculations to explore the σ-hole interaction properties of small-molecule compounds containing divalent sulfur. CSD surveys showed that 7095 structures contained R 1—S—R 2 groups that interact with electronegative atoms like N, O, S and Cl. Frequencies of occurrence and geometries of the interaction were dependent on the nature of R 1 and R 2, and the hybridization of carbon atoms in C,C—S, and C,S—S fragments. The most common interactions in terms of frequency of occurrence were C,C—S...O, C,C—S...N and C,C—S...S with predominance of Csp 2. The strength of the chalcogen interaction increased when enhancing the electron-withdrawing character of the substituents. The most positive electrostatic potentials (V S,max; illustrating positive σ-holes) calculated on R 1—S—R 2 groups were located on the S atom, in the S—R 1 and S—R 2 extensions, and increased with electron-withdrawing R 1 and R 2 substituents like the interaction strength did. As with geometric data derived from the CSD, interaction geometries calculated for some model systems and representative CSD compounds suggested that the interactions were directed in the extensions of S—R 1 and S—R 2 bonds. The values of complexation energies supported attractive interactions between σ-hole bond donors and acceptors, enhanced by dispersion. The interactions of R 1—S—R 2 with large V S,max and nucleophiles with large negative V S,min coherently provided more negative energies. According to NBO analysis, chalcogen interactions consisted of charge transfer from a nucleophile lone pair to an S—R 1 or S—R 2 antibonding orbital. The directional σ-hole interactions at R 1—S—R 2 can be useful in crystal engineering and the area of supramolecular biochemistry.

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Section: Discussionmentioning

confidence: 99%

σ-Hole interactions in small-molecule compounds containing divalent sulfur groupsR₁—S—R₂

Lundemba

Bibelayi

Wood

et al. 2020

Acta Crystallogr B Struct Sci Cryst Eng Mater

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“…Crystals 2020, 10, 180 14 of 28 A noble gas (or aerogen) [236] bond (NgB) was recently defined as: the interaction between an electron rich atom or group of atoms and any element of Group-18 acting as electron acceptor [237]. While reports on π,σ-hole interactions involving atoms of groups 14 to 17 as LA have exponentially grown in recent years, investigations on experimental aerogen bonding are scarce.…”

Section: Aerogen Bondsmentioning

confidence: 99%

Not Only Hydrogen Bonds: Other Noncovalent Interactions

2020

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In this review, we provide a consistent description of noncovalent interactions, covering most groups of the Periodic Table. Different types of bonds are discussed using their trivial names. Moreover, the new name “Spodium bonds” is proposed for group 12 since noncovalent interactions involving this group of elements as electron acceptors have not yet been named. Excluding hydrogen bonds, the following noncovalent interactions will be discussed: alkali, alkaline earth, regium, spodium, triel, tetrel, pnictogen, chalcogen, halogen, and aerogen, which almost covers the Periodic Table entirely. Other interactions, such as orthogonal interactions and π-π stacking, will also be considered. Research and applications of σ-hole and π-hole interactions involving the p-block element is growing exponentially. The important applications include supramolecular chemistry, crystal engineering, catalysis, enzymatic chemistry molecular machines, membrane ion transport, etc. Despite the fact that this review is not intended to be comprehensive, a number of representative works for each type of interaction is provided. The possibility of modeling the dissociation energies of the complexes using different models (HSAB, ECW, Alkorta-Legon) was analyzed. Finally, the extension of Cahn-Ingold-Prelog priority rules to noncovalent is proposed.

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“…[6,7] According to the type of atom with which the σ-hole is associated, these interactions are divided into hydrogen bond (HB), [8][9][10] halogen bond (XB), [11][12][13] pnicogen bond, [14][15][16] chalcogen bond, [17][18][19] tetrel bond (TB) [20][21][22][23][24] and nobel gas bond (NgB). [25] Among them, H-bonding is arguably the most important and widespread noncovalent interaction. The sobriquet of "tetrel bond" was proposed by Bauzá et al in 2013 [20] for the interaction that had been discussed earlier [26][27][28] for interactions involving the C, Si etc family.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Competition between Hydrogen and Tetrel Bonds by a Magnesium Bond

2020

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A computational study of the complexes formed by TF 3 OH (T=C, Si, Ge) with three nitrogen-containing bases NCH, NH 3 , and imidazole (IM) is carried out at the MP2/aug-cc-pVTZ level. TF 3 OH can participate in two different types of noncovalent interactions: a hydrogen bond (HB) involving the hydroxyl proton and a tetrel bond (TB) with the tetel atom T. The strength of the HB is largely unaffected by the identity of T while the TB is enhanced as T grows larger. The HB is preferred over the TB for most systems, with the exception of GeF 3 OH with either NH 3 or IM. MgCl 2 engages in a Mg···O Magnesium bond (Mg-bond) with the TF 3 OH O atom, which cooperatively enhances both the HB and TB. The HB strengthening is particularly large for the NH 3 or IM bases, and especially for CF 3 OH, but is slowly reduced as the T atom grows larger. The TB enhancement, on the other hand, behaves in the opposite fashion, accelerating for the larger T atoms. As a bottom line, the Mg-bond generally reinforces and accentuates the preference for the HB or TB that is already present in the dimer. The Mg-bond is also responsible for a proton transfer in the HB configurations with NH 3 and IM.[a] Dr.

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σ/π-Hole noble gas bonding interactions: Insights from theory and experiment

Cited by 95 publications

References 115 publications

σ-Hole interactions in small-molecule compounds containing divalent sulfur groupsR₁—S—R₂

σ-Hole interactions in small-molecule compounds containing divalent sulfur groupsR₁—S—R₂

Not Only Hydrogen Bonds: Other Noncovalent Interactions

Tuning the Competition between Hydrogen and Tetrel Bonds by a Magnesium Bond

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σ/π-Hole noble gas bonding interactions: Insights from theory and experiment

Cited by 95 publications

References 115 publications

σ-Hole interactions in small-molecule compounds containing divalent sulfur groupsR1—S—R2

σ-Hole interactions in small-molecule compounds containing divalent sulfur groupsR1—S—R2

Not Only Hydrogen Bonds: Other Noncovalent Interactions

Tuning the Competition between Hydrogen and Tetrel Bonds by a Magnesium Bond

Contact Info

Product

Resources

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σ-Hole interactions in small-molecule compounds containing divalent sulfur groupsR₁—S—R₂

σ-Hole interactions in small-molecule compounds containing divalent sulfur groupsR₁—S—R₂