Dataset Information

On the Potentiality of X-T-X₃ Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors.

ABSTRACT: The versatility of the X-T-X₃ compounds (where T = C, Si, and Ge, and X = F, Cl, and Br) to participate in tetrel- and halogen-bonding interactions was settled out, at the MP2/aug-cc-pVTZ level of theory, within a series of configurations for (X-T-X₃)₂ homodimers. The electrostatic potential computations ensured the remarkable ability of the investigated X-T-X₃ monomers to participate in σ-hole halogen and tetrel interactions. The energetic findings significantly unveil the favorability of the tetrel···tetrel directional configuration with considerable negative binding energies over tetrel···halogen, type III halogen···halogen, and type II halogen···halogen analogs. Quantum theory of atoms in molecules and noncovalent interaction analyses were accomplished to disclose the nature of the tetrel- and halogen-bonding interactions within designed configurations, giving good correlations between the total electron densities and binding energies. Further insight into the binding energy physical meanings was invoked through using symmetry-adapted perturbation theory-based energy decomposition analysis, featuring the dispersion term as the most prominent force beyond the examined interactions. The theoretical results were supported by versatile crystal structures which were characterized by the same type of interactions. Presumably, the obtained findings would be considered as a solid underpinning for future supramolecular chemistry, materials science, and crystal engineering studies, as well as a fundamental linchpin for a better understanding of the biological activities of chemicals.

SUBMITTER: Ibrahim MAA

PROVIDER: S-EPMC8320108 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature

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Publications

On the Potentiality of X-T-X3 Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors.

Ibrahim Mahmoud A A MAA Moussa Nayra A M NAM Soliman Mahmoud E S MES Moustafa Mahmoud F MF Al-Fahemi Jabir H JH El-Mageed H R Abd HRA

ACS omega 20210716 29

The versatility of the X-T-X3 compounds (where T = C, Si, and Ge, and X = F, Cl, and Br) to participate in tetrel- and halogen-bonding interactions was settled out, at the MP2/aug-cc-pVTZ level of theory, within a series of configurations for (X-T-X3)2 homodimers. The electrostatic potential computations ensured the remarkable ability of the investigated X-T-X3 monomers to participate in σ-hole halogen and tetrel interactions. The energetic findings si ...[more]

PMID: 34337270

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Project description:Recently, noncovalent interactions in complexes and crystals have attracted considerable interest. The current study was thus designed to gain a better understanding of three seminal types of noncovalent interactions, namely: hydrogen, halogen and tetrel interactions with π-systems. This study was performed on three models of Lewis acids: X3-C-H, F3-C-X and F-T-F3 (where X = F, Cl, Br and I; and T = C, Si, Ge and Sn) and three π-systems as Lewis bases: benzene (BZN), 1,3,5-trifluorobenzene (TFB) and hexafluorobenzene (HFB). Quantum mechanical calculations, including geometrical optimization, molecular electrostatic potential (MEP), maximum positive electrostatic potential (V s,max), Point-of-Charge (PoC), potential energy surface (PES), quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) calculations, were carried out at the MP2/aug cc-pVDZ level of theory. The binding energies were additionally benchmarked at the CCSD(T)/CBS level. The results showed that: (i) the binding energies of the X3-C-H⋯π-system complexes were unexpectedly inversely correlated with the V s,max values on the hydrogen atom but directly correlated with the X atomic sizes; (ii) the binding energies for the F3-C-X⋯π-system and F-T-F3⋯π-system complexes were correlated with the σ-hole magnitudes of the X and T atoms, respectively; and (iii) for the F3-C-F⋯π-system complexes, the binding energy was as strong as the π-system was electron-deficient, indicating the dominating nucleophilic character of the fluorine atom. NCI analysis showed that the unexpected trend of X3-C-H⋯π-system binding energies could be attributed to additional attractive interactions between the X atoms in the X3-C-H molecule and the carbon atoms of the π-system. Furthermore, the I3-Sn-H molecule was employed as a case study of hydrogen, halogen and tetrel interactions with π-systems. It was found that hydrogen and halogen interactions of the I3-Sn-H molecule correlated with the electron-richness of the π-system. In contrast, tetrel interactions correlated with the electron deficiency of the π-system.

Project description:The behavior of a sterically crowded neutral pincer {2,6-bis[(di-t-butylphosphino)methyl]-phenyl}palladium (PCPPd) halides, PCPPdX (X = Cl, Br or I), as XB acceptors with strong halogen bond (XB) donors, iodine (I(2)), 1,4-diiodotetrafluorobenzene (F4DIBz), and 1,4-diiodooctafluorobutane (F8DIBu) were studied in the solid state. The co-crystallization experiments afforded high-quality single crystals of XB complexes PCPPdCl-I(2) (1a), PCPPdBr-I(2) (2a), PCPPdI-I(2)(3a), PCPPdCl-F4DIBz (1b), PCPPdBr-F4DIBz (2b), and PCPPdBr-F8DIBu (2c). The 1:1 iodine complexes (1a, 2a, and 3a) all showed a strong halogen bonding interaction, the reduction of the sum of the van der Waals radii of halogen to iodine being 24.6 (1a), 23.9 (2a), and 19.4% (3a) with X···I-I angles of 177, 176, and 179°, respectively. While the pincer palladium chloride 1 and bromide 2 were crystallographically isomorphous and showed similar XB behavior, the palladium iodide complex, 3, exhibited markedly different properties, and unlike 1 and 2 it does not, under similar conditions, result in XB complexes with the weaker XB donors F4DIBz and F8DIBu. The results indicate that PCPPdI is not nucleophilic enough to have XB interactions with other donors than iodine. However, the weaker XB donors F4DIBz and F8DIBu form XB complexes with the chloride 1 and especially with the bromide 2. The prevalence of the halogen bonding with 2 is probably not only electronic in origin, and it seems to offer the best balance between electron poorness and steric availability. The XB interactions with F4DIBz and F8DIBu are much weaker than with iodine, the reduction of the sum of the van der Waals radii of halogen to iodine being 13.5, 12.3, and 14.6% with C-I···X angles between 163 and 179° for 1b, 2b, and 2c, respectively, and results in polymeric (···1···F4DIBz···1···F4DIBz···)(n), (···2···F4DIBz···2···F4DIBz···)(n), and (···2···F8DIBu···2···F8DIBu···)(n) one-dimensional zigzag chains in the solid state.

Dataset Information

On the Potentiality of X-T-X₃ Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors.

Publications

On the Potentiality of X-T-X<sub>3</sub> Compounds (T = C, Si, and Ge, and X = F, Cl, and Br) as Tetrel- and Halogen-Bond Donors.

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