Nature and strength of chalcogen–π bonds

Bortoli, Marco; Ahmad, Shah Masood; Hamlin, Trevor A.; Bickelhaupt, F. Matthias; Orian, Laura

doi:10.1039/c8cp05922e

Cited by 28 publications

(16 citation statements)

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“…And indeed, there have been numerous studies that demonstrated this principle. [52][53][54][55][56][57][58] In one example, Riley et al [56][57][58] demonstrated that substitution of heavier central halogens leads to a larger σ-hole and consequently to a stronger interaction, more electrostatic in nature. Politzer and Murray 25 presented, in turn, a correlation between σ-hole intensity and interaction energies for 18 halogen bonded complexes with NCH.…”

Section: Introductionmentioning

confidence: 99%

Influence of monomer deformation on the competition between two types of σ-holes in tetrel bonds

Wysokiński

Michalczyk

Zierkiewicz

et al. 2019

Phys. Chem. Chem. Phys.

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Section: Introductionmentioning

confidence: 99%

Influence of monomer deformation on the competition between two types of σ-holes in tetrel bonds

Wysokiński

Michalczyk

Zierkiewicz

et al. 2019

Phys. Chem. Chem. Phys.

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“…Results obtained with the cheap OLYP functional are also considered to assess the error when tackling these systems with a pure GGA functional. Both OLYP and BLYP‐D3(BJ) have been employed successfully for mechanistic studies involving methyl‐ and aryl‐chalcogenides 49,56–58 …”

Section: Resultsmentioning

confidence: 99%

Chalcogen–mercury bond formation and disruption in model Rabenstein's reactions: A computational analysis

et al. 2020

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Methylmercury is a highly toxic compound and human exposure is mainly related to consumption of polluted fish and seafood. The inactivation of thiol-based enzymes, promoted by the strong affinity binding of electrophilic mercuric ions to thiol and selenol groups of proteins, is likely an important factor explaining its toxicity. A key role is played by the chemistry and reactivity of the mercury-chalcogens bond, particularly Hg S and Hg Se, which is the focus of this computational work (level of theory: (COSMO)-ZORA-BLYP-D3(BJ)/TZ2P). We analyze nine ligand-exchange model reactions (the so-called Rabenstein's reactions) involving an entering ligand (methylchalcogenolate) and a substrate (methylchalcogenolatemethylmercury). Trends in reaction and activation energies are discussed and a change in mechanism is reported for all cases when going from gas phase to water, that is, from a single-well potential energy surface (PES) to a canonical S N 2-like mechanism. The reasons accounting for the biochemically challenging and desired displacement of methylmercury from a seleno/ thiol protein can be found already in these model reactions, as can be seen from the similarities of the ligand exchange reactions in solution in thermodynamics and kinetics.

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“…Another application is the study of chalcogen bonding. Depending on the type of chalcogen interaction at hand, electrostatics, orbital interactions, or dispersion can be dominant. Typically, orbital interactions are studied by various methods including NBO and EDA‐NOCV .…”

Section: Resultsmentioning

confidence: 99%

A Universal Quantitative Descriptor of the Dispersion Interaction Potential

Pollice

Chen

2019

Angewandte Chemie

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London dispersion, universally attractive forces originating from fluctuating dipoles,i so mnipresent in molecules.W hile its understanding has recently made tremendous progress,i ts general appreciation is still lagging behind electrostatics.T his can be explained by the simple tools available to study electrostatic interactions,such as electrostatic potential (ESP) maps and partial charges,a nd al ackt hereof for dispersion. We herein report au niversal quantitative descriptor of dispersion interaction potentials,w hicha llows assessing dispersion visually by London dispersion potential (LDP) maps,and quantitatively using the average LDP on the van der Waals surface.W edemonstrate the utility of these new tools by constructing aq uantitative dispersion energy scale of the elements and common substituents,s tudying non-covalent interactions (NCIs), and developing modern linear free energy relationships in catalysis.

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Nature and strength of chalcogen–π bonds

Abstract: We have analyzed the chalcogen–π bonding mechanism in a systematic series of model systems through Kohn–Sham molecular orbital theory and a quantitative energy decomposition scheme.

Cited by 28 publications

References 50 publications

Influence of monomer deformation on the competition between two types of σ-holes in tetrel bonds

Influence of monomer deformation on the competition between two types of σ-holes in tetrel bonds

Chalcogen–mercury bond formation and disruption in model Rabenstein's reactions: A computational analysis

A Universal Quantitative Descriptor of the Dispersion Interaction Potential

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