Tetravalent Oxygen and Sulphur Centres Mediated by Carborane Superacid: Theoretical Analysis

Grabowski, Sławomir J.; Casanova, David; Formoso, Elena; Ugalde, Jesús M.

doi:10.1002/cphc.201900687

Cited by 9 publications

(8 citation statements)

References 47 publications

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“…Thus, one can see that the scheme presented there may be extended on other configurations, and that other interactions may be inserted there since only few examples are presented in this figure. One example of the protonation of the water molecule may be mentioned, H 2 O + H + → H 3 O + + H + → H 4 O 2+ [ 131 ], which corresponds to the following changes of conformations: AX 2 E 2 → AX 3 E → AX 4 . The latter example concerns the change of the conformation of the Lewis base centre (oxygen) while the whole classification related to the VSEPR approach proposed here is based on changes of conformations of interacting Lewis acid centres.…”

Section: The Hydrogen Bond and The Halogen Bond Related To Vsepr Modelmentioning

confidence: 99%

Classification of So-Called Non-Covalent Interactions Based on VSEPR Model

Grabowski

2021

Molecules

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The variety of interactions have been analyzed in numerous studies. They are often compared with the hydrogen bond that is crucial in numerous chemical and biological processes. One can mention such interactions as the halogen bond, pnicogen bond, and others that may be classified as σ-hole bonds. However, not only σ-holes may act as Lewis acid centers. Numerous species are characterized by the occurrence of π-holes, which also may play a role of the electron acceptor. The situation is complicated since numerous interactions, such as the pnicogen bond or the chalcogen bond, for example, may be classified as a σ-hole bond or π-hole bond; it ultimately depends on the configuration at the Lewis acid centre. The disadvantage of classifications of interactions is also connected with their names, derived from the names of groups such as halogen and tetrel bonds or from single elements such as hydrogen and carbon bonds. The chaos is aggravated by the properties of elements. For example, a hydrogen atom can act as the Lewis acid or as the Lewis base site if it is positively or negatively charged, respectively. Hence names of the corresponding interactions occur in literature, namely hydrogen bonds and hydride bonds. There are other numerous disadvantages connected with classifications and names of interactions; these are discussed in this study. Several studies show that the majority of interactions are ruled by the same mechanisms related to the electron charge shifts, and that the occurrence of numerous interactions leads to specific changes in geometries of interacting species. These changes follow the rules of the valence-shell electron-pair repulsion model (VSEPR). That is why the simple classification of interactions based on VSEPR is proposed here. This classification is still open since numerous processes and interactions not discussed in this study may be included within it.

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Section: The Hydrogen Bond and The Halogen Bond Related To Vsepr Modelmentioning

confidence: 99%

Classification of So-Called Non-Covalent Interactions Based on VSEPR Model

Grabowski

2021

Molecules

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“…The parent compound (closo-B 10 H 12 C 2 ) has three different isomers depending on the relative disposition of the compound (closo-B10H12C2) has three different isomers depending on the relative disposition of the carbon atoms: ortho (closo-1,2-dicarbadodecarborane), meta (closo-1,7-dicarbadodecarborane) and para (closo-1,12-dicarbadodecarborane) (Scheme 1). Theoretical studies of the interaction of carboranes with biomolecules by means of dihydrogen bonds [50], the hydrogen bond with π-systems [51,52], halogen bonds [53,54], interaction with gold derivatives [55,56] and as superacids [57] In this article, we studied the complexes between a Lewis base, hydrogen cyanide (NCH), used as a hydrogen bond (HB) and halogen bond (XB) acceptor probe and 1-halo-closo-carboranes (Scheme 2) acting as hydrogen-and halogen-bond donors. The parent compounds X = H have also been considered.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen vs. Halogen Bonds in 1-Halo-Closo-Carboranes

2020

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A theoretical study of the hydrogen bond (HB) and halogen bond (XB) complexes between 1-halo-closo-carboranes and hydrogen cyanide (NCH) as HB and XB probe has been carried out at the MP2 computational level. The energy results show that the HB complexes are more stable than the XBs for the same system, with the exception of the isoenergetic iodine derivatives. The analysis of the electron density with the quantum theory of atoms in molecules (QTAIM) shows the presence of a unique intermolecular bond critical point with the typical features of weak noncovalent interactions (small values of the electron density and positive Laplacian and total energy density). The natural energy decomposition analysis (NEDA) of the complexes shows that the HB and XB complexes are dominated by the charge-transfer and polarization terms, respectively. The work has been complemented with a search in the CSD database of analogous complexes and the comparison of the results, with those of the 1-halobenzene:NCH complexes showing smaller binding energies and larger intermolecular distances as compared to the 1-halo-closo-carboranes:NCH complexes.

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“…When H 3 O + was present in the system, H 3 O + can form H 4 O + and H 2 O, releasing one Eh to the system (Figure 2G). Although tetravalent oxygen can exist in superacids, 49,50 the formation of H 4 O + may be an artifact of the simulation. Because only one H 4 O + is formed in the presence of 15 H 3 O + , the reaction tends to be concentration‐dependent, and the formation of H 4 O + was not observed at low concentrations(Figure 2K,L), supporting this assumption.…”

Section: Resultsmentioning

confidence: 99%

Valence energy correction for electron reactive force field

Bertolini

Jacob

2022

J Comput Chem

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Reactive force fields (ReaxFF) are a classical method to describe material properties based on a bond‐order formalism, that allows bond dissociation and consequently investigations of reactive systems. Semiclassical treatment of electrons was introduced within ReaxFF simulations, better known as electron reactive force fields (eReaxFF), to explicitly treat electrons as spherical Gaussian waves. In the original version of eReaxFF, the electrons and electron–holes can lead to changes in both the bond energy and the Coulomb energy of the system. In the present study, the method was modified to allow an electron to modify the valence energy, therefore, permitting that the electron's presence modifies the three‐body interactions, affecting the angle among three atoms. When a reaction path involving electron transfer is more sensitive to the geometric configuration of the molecules, corrections in the angular structure in the presence of electrons become more relevant; in this case, bond dissociation may not be enough to describe a reaction path. Consequently, the application of the extended eReaxFF method developed in this work should provide an improved description of a reaction path. As a first demonstration this semiclassical force field was parametrized for hydrogen and oxygen interactions, including water and water's ions. With the modified methodology both the overall accuracy of the force field but also the description of the angles within the molecules in presence of electrons could be improved.

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Tetravalent Oxygen and Sulphur Centres Mediated by Carborane Superacid: Theoretical Analysis

Cited by 9 publications

References 47 publications

Classification of So-Called Non-Covalent Interactions Based on VSEPR Model

Classification of So-Called Non-Covalent Interactions Based on VSEPR Model

Hydrogen vs. Halogen Bonds in 1-Halo-Closo-Carboranes

Valence energy correction for electron reactive force field

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