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Wiązanie trielowe, tetrelowe, pnikogenowe, chalkogenowe, halogenowe, aerogenowe : oddziaływania niekowalencyjne pierwiastków bloku P

Zierkiewicz Wiktor, Michalczyk Mariusz

Wiadomości Chemiczne

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2020

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[Z] 74, 9-10

587--607

EN

It is widely accepted that hydrogen bonds contribute into a variety of meaningful processes in nature and human body which has reflection in the share of the scientific community attention over the last decades. Recent years have seen a veritable explosion of research into noncovalent interactions that are analogous to the commonly acknowledged H-bonds. It became obvious that detailed investigation of these types of short contacts should be extensively considered as the main target for theoretical chemistry. In 2007 the article described the σ-hole concept enlightened the phenomena of the halogen bond. Later extensions of this concept into the other elements in periodic table provided the necessary knowledge about the origin of these interactions and gave arise for introducing the other members of the σ-hole bonds family as the chalcogen, pnicogen, tetrel and triel bonds or even those involving noble gases. The foundation of the σ-hole theory is the presence of the region of thinned electronic density caused by the anisotropic accumulation of the negative charge on the covalent R-X bond (where X=halogen) what causes the rising of positive electrostatic potential on the outer side of X atom. This particular location becomes the binding site for the approaching nucleophile. As the σ-hole is located in plane of molecule on an extension of covalent bond, some molecules also contain a σ-hole region situated above and below the plane of the molecular framework. In current work the representative examples of complexes bonded through the σ- or π-holes and their most important features have been briefly given. The main goal was to show the diversity of this type of interaction which covers nearly all the elements of the block p of periodic table. Triel bonds are produced mainly by -hole interaction with Lewis bases and can be characterized by different nature for different elements (boron complexes are stabilized by electrostatics and charge transfer, while Al and Ga ones mostly by electrostatics). In tetrel, pnicogen and chalcogen bonded complexes it has been shown that during the process of dimerization the substantial geometric distortion is observed on the π-hole donor molecules. It causes the creation of the second complexation path through newly created π-hole. In chalcogen bonded complexes the alternative dimer is stabilized by π-hole and something like - due to presence of lone electron pair of chalcogen. Within the halogen bonds one can highlight the issue of weakening the negative hyperconjugation on the molecules of methylated derivatives of ammonia (like methylamine). It is caused by the appearing of σ-hole donor (FCCl3) which takes control of the majority part of intramolecular charge transfer and in this way enhances the link between subunits at the price of hampering the internal conjugation. Finally, the short report of aerogen bonds in literature is inserted in the last chapter of current paper. Some molecules with noble gases connected with highly electron-withdrawing constituents are able to generate both: σ- and π-hole on their surfaces and in consequences the stable complexes with Lewis bases (for example, diazines). The presence of the latter proves that the discussed types of interaction are very common for massive amount of atoms, even for those which are considered as less reactive.

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Wiązania chalkogenowe : początki oraz znaczenie w układach biologicznych

Bucka Alicja, Dopieralski Przemysław

Wiadomości Chemiczne

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2020

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[Z] 74, 9-10

663--686

EN

The chalcogen bond is analogous to the halogen and hydrogen bond and it produces favorable interactions between 16th group of elements, that play a role in catalysis, medical chemistry, design of materials and biological processes. In the solid state, the chalcogen bond was used to build nano-sized structures and in solution is responsible mainly for intramolecular interactions, which stabilize the structures of intermediates and reagents. Recently, chalcogen bonds have been increasingly used in the recognition and transport of anions and in organic synthesis.

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Borowce jako centra kwasów Lewisa w oddziaływaniach międzycząsteczkowych : porównanie z wiązaniami wodorowymi

Grabowski S. J.

Wiadomości Chemiczne

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2017

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[Z] 71, 7-8

447--471

EN

The triel bonds are analyzed and compared with the hydrogen bond interaction. The triel bonds belong to the class of interactions that are named as the σ-hole and π-hole bonds. The σ-hole bond is an interaction between the σ-hole characterized by the positive electrostatic potential and the electron rich regions such as lone electron pairs, π-electron systems, in other words, centers paying a role of Lewis bases. The σ-holes may be observed for elements of the 14–18 groups of the periodic system and the corresponding interactions with Lewis bases are named; tetrel, pnicogen, chalcogen, halogen and aerogen bonds, respectively. On the other hand, π-holes also characterized by the positive electrostatic potential are observed for centers in planar molecules or planar fragments of molecules in regions above those planes. π-holes may be attributed to triel centers (13th group of the periodic system). The boron and aluminium trihydrides and trihalides are examples of molecules where triels are characterized by π-holes. The mechanism of the triel bond formation is very similar to the mechanism of the formation of the hydrogen bond. It is the Lewis acid – Lewis base interaction where the electron charge transfer from the base unit to the acid one is observed. Next there is outflow of the electron charge from the triel center to the other parts of the Lewis acid unit; in other words the positive charge of the triel center increases as a result of complexation. The triel bonds are often very strong and often they possess characteristics of typical covalent bonds; this is confirmed by the QTAIM (Quantum Theory of Atoms in Molecules) and NBO (Natural Bond Orbital) approaches. For example, for the triel bonds the bond paths between the triel center and the Lewis base center are observed with the bond critical points (BCPs) attributed to those paths. Similarly for the A-H…B hydrogen bonds the H…B bond paths are observed. The parameters of those BCPs often indicate the covalent character of the triel bonds and analogously those characteristics for H-bonds may also indicate the covalent character of the latter interactions. It is very interesting that the triel bonds are observed experimentally in the real systems; for example in crystal structures. The triel center which is trivalent and possesses the trigonal configuration is hypovalent; it means that the octet rule is not obeyed here because of the valence electrons´ deficiency (the triel center possesses six valence electrons in such species). Thus it may interact with one Lewis base ligand reaching rather stable octet and tetrahedral configuration. If the trivalent triel center interacts with two Lewis base ligands thus it may lead to the configuration of the trigonal bipyramid with the hypervalent and pentavalent triel center. These kinds of the triel species occur in crystal structures that are described here.