Halogen Bonds Formed between Substituted Imidazoliums and N Bases of Varying N-Hybridization

Scheiner, Steve

doi:10.3390/molecules22101634

Cited by 22 publications

(16 citation statements)

References 104 publications

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“…Other contributions arising from exchange repulsion and dispersion play important roles in determining the equilibrium geometry of a chemical system. The same point has been made previously, especially in the context of halogen bonding [36,38,[96][97][98][99][100].…”

Section: Resultssupporting

confidence: 67%

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Varadwaj

Marques

et al. 2018

Computation

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The divergence of fluorine-based systems and significance of their nascent non-covalent chemistry in molecular assemblies are presented in a brief review of the field. Emphasis has been placed to show that type-I and -II halogen-centered F···F long-ranged intermolecular distances viable between the entirely negative fluorine atoms in some fluoro-substituted dimers of C 6 H 6 can be regarded as the consequence of significant non-covalent attractive interactions. Such attractive interactions observed in the solid-state structures of C 6 F 6 and other similar fluorine-substituted aromatic compounds have frequently been underappreciated. While these are often ascribed to crystal packing effects, we show using first-principles level calculations that these are much more fundamental in nature. The stability and reliability of these interactions are supported by their negative binding energies that emerge from a supermolecular procedure using MP2 (second-order Møller-Plesset perturbation theory), and from the Symmetry Adapted Perturbation Theory, in which the latter does not determine the interaction energy by computing the total energy of the monomers or dimer. Quantum Theory of Atoms in Molecules and Reduced Density Gradient Non-Covalent Index charge-density-based approaches confirm the F···F contacts are a consequence of attraction by their unified bond path (and bond critical point) and isosurface charge density topologies, respectively. These interactions can be explained neither by the so-called molecular electrostatic surface potential (MESP) model approach that often demonstrates attraction between sites of opposite electrostatic surface potential by means of Coulomb's law of electrostatics, nor purely by the effect of electrostatic polarization. We provide evidence against the standalone use of this approach and the overlooking of other approaches, as the former does not allow for the calculation of the electrostatic potential on the surfaces of the overlapping atoms on the monomers as in the equilibrium geometry of a complex. This study thus provides unequivocal evidence of the limitation of the MESP approach for its use in gaining insight into the nature of reactivity of overlapped interacting atoms and the intermolecular interactions involved.

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Section: Resultssupporting

confidence: 67%

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Varadwaj

Marques

et al. 2018

Computation

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“…One can obtain an alternate view of the strength of the intermolecular interaction via AIM analysis of the topography of the electron density of each complex. In particular, the density at the bond critical point connecting a pair of atoms is thought to be directly related to the strength of the noncovalent bond 25,[95][96][97][98][99][100][101][102][103][104][105] . This quantity is reported as ρBCP in Table 2.…”

Section: Analysis Of Wave Functionsmentioning

confidence: 99%

Steric Crowding in Tetrel Bonds

Scheiner

2018

J. Phys. Chem. A

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The tetravalent character of tetrel atoms leaves only limited room for an incoming nucleophile to approach and engage in a noncovalent bond with a tetrel atom. Any such approach can only occur at the expense of internal geometric distortions. The balance between attractive forces and repulsive steric crowding was studied for a series of Lewis acids of the type FTR (T = Si, Ge, Sn, Pb) which were allowed to interact with various bases. The strength and other properties of the tetrel bond are examined as the R groups are made progressively larger, varying from H and CH to isopropyl and tert-butyl, which induce steric crowding with the incoming base. The effects of crowding which impede the bond can be offset by enlarging the T atom, by adding electron-withdrawing substituents to the Lewis acid, or by considering stronger bases such as anions. The tetrel bond energies reach up to 10 kcal/mol for a pair of neutral molecules with no electron-withdrawing substituents on the Lewis acid. Adding -CF substituents grows the interaction energy to as high as 35 kcal/mol, and a further increment occurs for an anionic base, taking the maximum up to 54 kcal/mol.

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“…The problem of identification and categorization of different types of noncovalent bonds arose a long time ago (Desiraju & Parthasarathy, 1989;Metrangolo & Resnati, 2001;Legon, 2010;Scheiner, 2011;Bauzá et al, 2017). The geometrical description indirectly treats the interactions in terms of angles and distances shorter than the sum of van der Waals radii.…”

Section: Introductionmentioning

confidence: 99%

Electronic criterion for categorizing the chalcogen and halogen bonds: sulfur–iodine interactions in crystals

Барташевич

Mukhitdinova

Yushina

et al. 2019

Acta Crystallogr B Struct Sci Cryst Eng Mater

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Diversity of mutual orientations of Y-S and I-X and covalent bonds in molecular crystals complicate categorizing noncovalent chalcogen and halogen bonds. Here, the different types of SÁ Á ÁI interactions with short interatomic distances are analysed. The selection of SÁ Á ÁI interactions for the categorization of the chalcogen and halogen bonds has been made using angles that determine the mutual orientation of electron lone pairs and -holes interacted S and I atoms. In complicated cases of noncovalent interactions with 'hole-to-hole' of S and I orientations, distinguishing the chalcogen and halogen bonds is only possible if the atom is uniquely determined, which also provides the electrophilic site. The electronic criterion for chalcogen/halogen bonds categorizing that is based on analysis of dispositions of electron density and electrostatic potential minima along the interatomic lines has been suggested and its effectiveness has been demonstrated.

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Halogen Bonds Formed between Substituted Imidazoliums and N Bases of Varying N-Hybridization

Cited by 22 publications

References 104 publications

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Steric Crowding in Tetrel Bonds

Electronic criterion for categorizing the chalcogen and halogen bonds: sulfur–iodine interactions in crystals

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