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

Molecules ◽  
2021 ◽  
Vol 26 (7) ◽  
pp. 2083
Author(s):  
Maxim L. Kuznetsov
Keyword(s):  
Bond Length ◽  
Interaction Energy ◽  
Electron Density ◽  
Halogen Bond ◽  
Bond Critical Point ◽  
Halogen Bonds ◽  
Curvature Potential ◽  
Non Covalent Interactions ◽  
Covalent Interactions

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.

scholarly journals Relationships between Interaction Energy and Electron Density Properties for Homo Halogen Bonds of the [(A)nY–X···X–Z(B)m] Type (X = Cl, Br, I)

Molecules ◽  
2019 ◽  
Vol 24 (15) ◽  
pp. 2733 ◽  
Author(s):  
Maxim L. Kuznetsov
Keyword(s):  
Kinetic Energy ◽  
Interaction Energy ◽  
Electron Density ◽  
Bond Critical Point ◽  
Kinetic Energy Density ◽  
Large Set ◽  
Halogen Bonds ◽  
Absolute Deviation ◽  
The Individual ◽  
Best Estimator

Relationships between interaction energy (Eint) and electron density properties at the X···X bond critical point or the d(X···X) distance were established for the large set of structures [(A)nY–X···X–Z(B)m] bearing the halogen bonds Cl···Cl, Br···Br, and I···I (640 structures in total). The best estimator of Eint is the kinetic energy density (Gb), which reasonably approximates the whole set of the structures as −Eint = 0.128Gb2 − 0.82Gb + 1.66 (R2 = 0.91, mean absolute deviation 0.39 kcal/mol) and demonstrates low dispersion. The potential and kinetic energy densities, electron density, and the d(X···X) distance behave similarly as estimators of Eint for the individual series Cl···Cl, Br···Br, and I···I. A number of the Eint(property) correlations are recommended for the practical application in the express estimates of the strength of the homo-halogen bonds.

Components of the interaction energy of the odd-electron halogen bond: an ab initio study

2020 ◽  
Vol 22 (27) ◽  
pp. 15389-15400
Author(s):  
Prasanta Bandyopadhyay ◽  
Md. Motin Seikh
Keyword(s):  
Ab Initio ◽  
Interaction Energy ◽  
Halogen Bond ◽  
Conceptual Dft ◽  
Ab Initio Study ◽  
Fertile Ground ◽  
Non Covalent Interactions ◽  
Covalent Interactions

The odd-electron halogen bond offers a fertile ground to explore the nature of non-covalent interactions. The regioselectivity, interaction energy and its components were analyzed by conceptual DFT parameters, NCI plot and LED-DLPNO-CCSD(T) analysis.

Experimental electron density study of the supramolecular aggregation between 4,4′-dipyridyl-N,N′-dioxide and 1,4-diiodotetrafluorobenzene at 90 K

2004 ◽  
Vol 60 (5) ◽  
pp. 559-568 ◽  
Author(s):  
Riccardo Bianchi ◽  
Alessandra Forni ◽  
Tullio Pilati
Keyword(s):  
Electron Density ◽  
Halogen Bond ◽  
X Ray Diffraction ◽  
One Dimensional ◽  
X Ray ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
Experimental Electron Density ◽  
Supramolecular Aggregation ◽  
Density Study

The electron density of the halogen-bonded complex of 4,4′-dipyridyl-N,N′-dioxide (bpNO) with 1,4-diiodotetrafluorobenzene (F4dIb) at 90 K has been determined by X-ray diffraction and analysed. The nature of the I...O intermolecular bond connecting the bpNO and F4dIb molecules into one-dimensional infinite chains, as well as the other non-covalent interactions present in the crystal, such as C—H...O, C—H...F and C—H...I hydrogen bonds and C...C, C...N, C...I and F...F interactions, have been investigated. The integration of electron density over the atomic basins reveals the electrostatic nature of the I...O halogen bond, which is very similar to a previously analysed I...N halogen bond.

scholarly journals The many flavours of halogen bonds – message from experimental electron density and Raman spectroscopy

2019 ◽  
Vol 75 (9) ◽  
pp. 1190-1201 ◽  
Author(s):  
Ruimin Wang ◽  
Janine George ◽  
Shannon Kimberly Potts ◽  
Marius Kremer ◽  
Richard Dronskowski ◽  
...  
Keyword(s):  
Critical Point ◽  
Electron Density ◽  
Halogen Bond ◽  
Bond Distance ◽  
Bond Critical Point ◽  
Halogen Bonds ◽  
Derived Properties ◽  
The Many ◽  
A Minor ◽  
Experimental Electron Density

Experimental electron-density studies based on high-resolution diffraction experiments allow halogen bonds between heavy halogens to be classified. The topological properties of the electron density in Cl...Cl contacts vary smoothly as a function of the interaction distance. The situation is less straightforward for halogen bonds between iodine and small electronegative nucleophiles, such as nitrogen or oxygen, where the electron density in the bond critical point does not simply increase for shorter distances. The number of successful charge–density studies involving iodine is small, but at least individual examples for three cases have been observed. (a) Very short halogen bonds between electron-rich nucleophiles and heavy halogen atoms resemble three-centre–four-electron bonds, with a rather symmetric heavy halogen and without an appreciable σ hole. (b) For a narrow intermediate range of halogen bonds, the asymmetric electronic situation for the heavy halogen with a pronounced σ hole leads to rather low electron density in the (3,−1) critical point of the halogen bond; the properties of this bond critical point cannot fully describe the nature of the associated interaction. (c) For longer and presumably weaker contacts, the electron density in the halogen bond critical point is only to a minor extent reduced by the presence of the σ hole and hence may be higher than in the aforementioned case. In addition to the electron density and its derived properties, the halogen–carbon bond distance opposite to the σ hole and the Raman frequency for the associated vibration emerge as alternative criteria to gauge the halogen-bond strength. We find exceptionally long C—I distances for tetrafluorodiiodobenzene molecules in cocrystals with short halogen bonds and a significant red shift for their Raman vibrations.

Tetrachloromethane as halogen bond donor toward metal-bound halides

2019 ◽  
Vol 234 (1) ◽  
pp. 9-17 ◽  
Author(s):  
Lev E. Zelenkov ◽  
Daniil M. Ivanov ◽  
Margarita S. Avdontceva ◽  
Alexander S. Novikov ◽  
Nadezhda A. Bokach
Keyword(s):  
Dft Calculations ◽  
Electron Density Distribution ◽  
Halogen Bond ◽  
Topological Analysis ◽  
Halogen Bonds ◽  
Chloride Complexes ◽  
X Ray ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
Supramolecular Contacts

Abstract Two annulated triazapentadiene systems, viz. 1,3,5,7,9-pentaazanona-1,3,6,8-tetraenate chloride complexes of PtII, form CCl4 solvates, containing the Cl3C–Cl···Cl–Pt halogen bonds. These halogen bonds are firstly reported type of Cl3C–Cl···Cl–M contacts. In the X-ray structures of two solvates different non-covalent interactions were detected and studied by DFT calculations and topological analysis of the electron density distribution within the framework of QTAIM method at the M06/DZP-DKH level of theory. Estimated energies of these supramolecular contacts vary from 0.6 to 2.4 kcal/mol.

Testing the tools for revealing and characterizing the iodine–iodine halogen bond in crystals

2017 ◽  
Vol 73 (2) ◽  
pp. 217-226 ◽  
Author(s):  
Ekaterina Bartashevich ◽  
Irina Yushina ◽  
Kristina Kropotina ◽  
Svetlana Muhitdinova ◽  
Vladimir Tsirelson
Keyword(s):  
Electron Density ◽  
Halogen Bond ◽  
Electron Shell ◽  
Electron Localization Function ◽  
Electron Localization ◽  
Localization Function ◽  
Non Covalent Interactions ◽  
The One ◽  
Covalent Interactions

To understand what tools are really suitable to identify and classify the iodine–iodine non-covalent interactions in solid organic polyiodides, we have examined the anisotropy of the electron density within the iodine atomic basin along and across the iodine–iodine halogen bond using the Laplacian of electron density, one-electron potential and electron localization function produced by Kohn–Sham calculations with periodic boundary conditions. The Laplacian of electron density exhibits the smallest anisotropy and yields a vague picture of the outermost electronic shells. The one-electron potential does not show such a deficiency and reveals that the valence electron shell for the halogen-bond acceptor iodine is always wider than that for the halogen-bond donor iodine along its σ-hole direction. We have concluded that the one-electron potential is the most suitable for classification of the iodine–iodine bonds and interactions in complicated cases, while the electron localization function allows to distinguish the diiodine molecule bonded with the monoiodide anion from the typical triiodide anion.

In Silico Characterization and Prediction of Thiourea-like Neutral Bidentate Halogen Bond Catalysts

2021 ◽  
Author(s):  
Hui Yang ◽  
Choon-Hong Tan ◽  
Ming Wah Wong
Keyword(s):  
In Silico ◽  
Halogen Bond ◽  
Steric Interaction ◽  
Halogen Bonds ◽  
Common Strategy ◽  
Non Covalent Interactions ◽  
Neutral Bidentate ◽  
In Silico Characterization ◽  
Covalent Interactions

Preorganization is a common strategy to align halogen bond (XB) donors to form two or more halogen bonds simultaneously. Previous approaches have utilized various non-covalent interactions such as steric interaction,...

scholarly journals "ANTI-HALOGEN" BONDS AS A FACTOR DETERMINING THE TETRAHEDRAL STRUCTURE OF COPPER IN ITS COMPLEXES WITH (5Z, 5'Z)-2,2'- (ETHANE-1,2-DIYLDISULFANYLDIYL)BIS(5-(2-PYRIDYLMETHYLENE)-3-ALLYL-3,5-DIHYDRO- 4H-IMIDAZOLE-4-ONE)

2021 ◽  
Vol 2 (74) ◽  
pp. 38-41
Author(s):  
A. Al-Khazraji ◽  
I. Dudkin ◽  
E. Ofitserov ◽  
A. Finko ◽  
E. Beloglazkina
Keyword(s):  
Electron Density ◽  
Copper Atom ◽  
Halogen Bond ◽  
Halogen Bonds ◽  
Tetrahedral Structure ◽  
Angle Of Rotation

Analysis of the valence angles of the Si and carbon atoms of the C-S bond in the obtained complexes of CiVg2 c (5Z, 5'Z)-2,2’-(ethane-1,2-diyldisulfanyldiyl)bis(5-(2-pyridylmethylene)-3-allyl-3,5-dihydro-4Нimidazole-4-one) unambiguously indicates the determinant effect of the non-valent interactions of the electron density centroids of the NEP of bromine atoms and sulfur atoms, leading to a change in the plane structure of Cu(II) towards tetrahedral with a likely change in the magnetochemical properties of the copper atom, and the angle of rotation of the planes is almost 900. This interaction is the opposite of what is commonly called a halogen bond. In this case, it is an "anti-halogen" bond.

scholarly journals New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

2016 ◽  
Vol 12 ◽  
pp. 2834-2848 ◽  
Author(s):  
Pavel Nagorny ◽  
Zhankui Sun
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Recent Progress ◽  
Halogen Bonds ◽  
Hydrogen Bond Donor ◽  
New Approaches ◽  
Substrate Activation ◽  
Non Covalent Interactions ◽  
Covalent Interactions ◽  
Hydrogen Bond Donors

Hydrogen bond donor catalysis represents a rapidly growing subfield of organocatalysis. While traditional hydrogen bond donors containing N–H and O–H moieties have been effectively used for electrophile activation, activation based on other types of non-covalent interactions is less common. This mini review highlights recent progress in developing and exploring new organic catalysts for electrophile activation through the formation of C–H hydrogen bonds and C–X halogen bonds.

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