The formation of H···X hydrogen bond, C···X carbon-halide or Si···X tetrel bonds on the silylene-halogen dimers (X = F or Cl): intermolecular strength, molecular orbital interactions and prediction of covalency

Oliveira, Boaz G.; Zabardasti, Abedien; Rego, Danilo Guimarães do; Pour, Mohsen Mohammad

doi:10.1007/s00214-020-02644-6

Cited by 6 publications

(3 citation statements)

References 127 publications

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“…In such a situation, an approximation of E b through other parameters easily accessible from experiment becomes very important [ 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 ]. Among these parameters, bond distance [ 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 , 77 , 78 ], electron density properties [ 61 , 79 , 80 , 81 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 , 96 , 97 , 98 , 99 , 100 , 101 , 102 , ...…”

Section: Introductionmentioning

confidence: 99%

Strength of the [Z–I···Hal]− and [Z–Hal···I]− Halogen Bonds: Electron Density Properties and Halogen Bond Length as Estimators of Interaction Energy

Kuznetsov

2021

Molecules

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Bond energy is the main characteristic of chemical bonds in general and of non-covalent interactions in particular. Simple methods of express estimates of the interaction energy, Eint, using relationships between Eint and a property which is easily accessible from experiment is of great importance for the characterization of non-covalent interactions. In this work, practically important relationships between Eint and electron density, its Laplacian, curvature, potential, kinetic, and total energy densities at the bond critical point as well as bond length were derived for the structures of the [Z–I···Hal]– and [Z–Hal···I]– types bearing halogen bonds and involving iodine as interacting atom(s) (totally 412 structures). The mean absolute deviations for the correlations found were 2.06–4.76 kcal/mol.

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Section: Introductionmentioning

confidence: 99%

Strength of the [Z–I···Hal]− and [Z–Hal···I]− Halogen Bonds: Electron Density Properties and Halogen Bond Length as Estimators of Interaction Energy

Kuznetsov

2021

Molecules

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“…This same phenomenon occurs on a divalent chalcogen Y atom, but each of its two RY bonds leads to a separate σ-hole, and a logical extension provides three σ-holes around a Z pnicogen atom in its ZR 3 configuration. Recent works [ 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ] have also included tetrel atoms T (C and Si, etc.) in this category, as the tetravalent TR 4 molecule has four σ-holes, so could, at least in principle, participate in as many as four simultaneous tetrel bonds.…”

Section: Introductionmentioning

confidence: 99%

Versatility of the Cyano Group in Intermolecular Interactions

Scheiner

2020

Molecules

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Several cyano groups are added to an alkane, alkene, and alkyne group so as to construct a Lewis acid molecule with a positive region of electrostatic potential in the area adjoining these substituents. Although each individual cyano group produces only a weak π-hole, when two or more such groups are properly situated, they can pool their π-holes into one much more intense positive region that is located midway between them. A NH3 base is attracted to this site, where it forms a strong noncovalent bond to the Lewis acid, amounting to as much as 13.6 kcal/mol. The precise nature of the bonding varies a bit from one complex to the next but typically contains a tetrel bond to the C atoms of the cyano groups or the C atoms of the linkage connecting the C≡N substituents. The placement of the cyano groups on a cyclic system like cyclopropane or cyclobutane has a mild weakening effect upon the binding. Although F is comparable to C≡N in terms of electron-withdrawing power, the replacement of cyano by F substituents substantially weakens the binding with NH3.

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“…Molecular crystal engineering relies on various types of intermolecular interactions competing to drive solid-state packing. While the strength of hydrogen bonding may dominate packing in structures where possible, the importance of other competing interactions has drawn increasing attention from a supramolecular perspective [1,2]. From C-H•••π [3] and π−π [4] to less studied chalcogen bonding [5] and halogen bonding [6], the roles and relative strengths of these previously considered weak interactions are now employed as key features in crystal packing design.…”

Section: Introductionmentioning

confidence: 99%

Halogen Interactions in Halogenated Oxindoles: Crystallographic and Computational Investigations of Intermolecular Interactions

et al. 2021

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X-ray structural determinations and computational studies were used to investigate halogen interactions in two halogenated oxindoles. Comparative analyses of the interaction energy and the interaction properties were carried out for Br···Br, C-H···Br, C-H···O and N-H···O interactions. Employing Møller–Plesset second-order perturbation theory (MP2) and density functional theory (DFT), the basis set superposition error (BSSE) corrected interaction energy (Eint(BSSE)) was determined using a supramolecular approach. The Eint(BSSE) results were compared with interaction energies obtained by Quantum Theory of Atoms in Molecules (QTAIM)-based methods. Reduced Density Gradient (RDG), QTAIM and Natural bond orbital (NBO) calculations provided insight into possible pathways for the intermolecular interactions examined. Comparative analysis employing the electron density at the bond critical points (BCP) and molecular electrostatic potential (MEP) showed that the interaction energies and the relative orientations of the monomers in the dimers may in part be understood in light of charge redistribution in these two compounds.

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The formation of H···X hydrogen bond, C···X carbon-halide or Si···X tetrel bonds on the silylene-halogen dimers (X = F or Cl): intermolecular strength, molecular orbital interactions and prediction of covalency

Cited by 6 publications

References 127 publications

Strength of the [Z–I···Hal]− and [Z–Hal···I]− Halogen Bonds: Electron Density Properties and Halogen Bond Length as Estimators of Interaction Energy

Strength of the [Z–I···Hal]− and [Z–Hal···I]− Halogen Bonds: Electron Density Properties and Halogen Bond Length as Estimators of Interaction Energy

Versatility of the Cyano Group in Intermolecular Interactions

Halogen Interactions in Halogenated Oxindoles: Crystallographic and Computational Investigations of Intermolecular Interactions

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