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The fragment of the crystal structure of N,N -bis(3-(dimethylamino)propyl) benzimidazolin-2-stannylene. The closest contacts are indicated, an intermolecular contact and an intramolecular one.
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The MP2/aug-cc-pVTZ calculations were performed on the dihalometallylenes to indicate their Lewis acid and Lewis base sites. The results of the Cambridge Structural Database search show corresponding and related crystal structures where the tetrel center often possesses the configuration of a trigonal bipyramid or octahedron. The calculations were...
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Context 1
... two Sn· · · O intermolecular contacts are formed with the trifluoromethanesulfonate molecules. Figure 3 presents the structure of N,N -bis(3-(dimethylamino)propyl)benzimidazolin-2-stannylene [42]. The tin center forms two bonds with nitrogen atoms here. ...
Context 2
... two Sn•••O intermolecular contacts are formed with the trifluoromethanesulfonate molecules. Figure 3 presents the structure of N,N'-bis(3-(dimethylamino)propyl)benzimidazolin-2-stannylene [42]. The tin center forms two bonds with nitrogen atoms here. ...
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We introduce a development of next generation quantum theory of atoms in molecules (NG-QTAIM) for an investigation of the chirality of ethane and discover a $Q_{\sigma}$ isomer in addition to $S_{\sigma}$ and $R_{\sigma}$ stereoisomers in the stress tensor trajectory $U_{\sigma}$-space. The $Q_{\sigma}$ isomer is defined to be a 'null-isomer' since...
Citations
... In addition to adding to our currently sparse knowledge about pentacoordinate C, the results will also inform our building knowledge base about noncovalent tetrel bonding. [9][10][11][12][13][14][15][16][17][18] ...
As a flat trigonal species, the CR3⁺ carbenium ion contains a pair of deep π‐holes above and below its molecular plane. In the case of CH3⁺ a first base will form a covalent bond with the central C, making the combined species tetrahedral. Approach of a second base to the opposite side results in a longer but rather strong noncovalent tetrel bond (TB). While CMe3⁺ can also form a similar asymmetric complex with a pair of bases, it also has the capacity to form a pair of nearly equivalent TBs, such that the resulting symmetric trigonal bipyramid configuration is only slightly higher in energy. When the three substituents on the central C are phenyl rings, the symmetric configuration with two TBs predominates. These tetrel bonds are quite strong, reaching up to 20 kcal/mol. Adding OPH2 or OCH substituents to the phenyl rings permits the formation of intramolecular C⋅⋅O TBs to the central C, very similar in many respects to the case where these TBs are intermolecular.
... This pattern continues with three σ-holes on the pnicogen Z atom of R 3 Z, [36][37][38][39][40][41][42] and four for a tetrel atom T in a R 4 T molecule. [28,[43][44][45][46][47][48][49][50][51][52] There has been a great deal of focused study of late that has helped to characterize each of these noncovalent bonds, and has shown a high dependency of the bond strength on the depth of the σ-hole, i. e. the positive molecular electrostatic potential (MEP) along the bond axis extension. [53] This depth is in turn heavily influenced by both the nature of the bridging A atom and any substituents R to which it is bonded. ...
The lone pair of the N atom is a common electron donor in noncovalent bonds. Quantum calculations examine how various aspects of the base on which the N is located affect the strength and other properties of complexes formed with Lewis acids FH, FBr, F2Se, and F3As that respectively encompass hydrogen, halogen, chalcogen, and pnicogen bonds. In most cases the halogen bond is the strongest, followed in order by chalcogen, hydrogen, and pnicogen. The noncovalent bond strength increases in the sp<sp²<sp³ order of hybridization of N. Replacement of H substituents on the base by a methyl group or substituting N by C atom to which the base N is attached, strengthens the bond. The strongest bonds occur for trimethylamine and the weakest for N2.
... First, the theoretical studies of TB interactions in which metallylenes act as Lewis bases are absent. Second, the theoretical studies of TB interactions in which metallylenes act as Lewis acids are sparse [65][66][67][68], and systematic studies involving all four metallylenes are still absent. Finally, it is informative to explore how the binding strength of TB interactions changes when the tetrel atoms become heavier. ...
The dual binding behavior of the metallylenes TH2 (T = Si, Ge, Sn, Pb) with some selected Lewis acids (T’H3F, T’ = Si, Ge, Sn, Pb) and bases (N2, HCN, CO, and C6H6) has been investigated by using the high-level quantum chemical method. Two types (type-A and type-B) of tetrel-bonded complexes can be formed for TH2 due to their ambiphilic character. TH2 act as Lewis bases in type-A complexes, and they act as Lewis acids in type-B ones. CO exhibits two binding modes in the type-B complexes, one of which is TH2···CO and the other is TH2···OC. The TH2···OC complexes possess a weaker binding strength than the other type-B complexes. The TH2···OC complexes are referred to as the type-B2 complexes, and the other type-B complexes are referred to as the type-B1 complexes. The type-A complexes exhibit a relatively weak binding strength with Eint (interaction energy) values ranging from –7.11 to –15.55 kJ/mol, and the type-B complexes have a broad range of Eint values ranging from −9.45 to −98.44 kJ/mol. The Eint values of the type-A and type-B1 complexes go in the order SiH2 > GeH2 > SnH2 > PbH2. The AIM (atoms in molecules) analysis suggests that the tetrel bonds in type-A complexes are purely closed-shell interactions, and those in most type-B1 complexes have a partially covalent character. The EDA (Energy decomposition analysis) results indicate that the contribution values of the three energy terms go in the order electrostatic > dispersion > induction for the type-A and type-B2 complexes, and this order is electrostatic > induction > dispersion for the type-B1 complexes.
... Ⱥɧɚɥɨɝɢɱɧɨɟ ɩɨɜɟɞɟɧɢɟ ɞɟɦɨɧɫɬɪɢɪɭɸɬ ɫɬɚɧɧɢɥɟɧɵ ɧɚ ɨɫɧɨɜɟ ɨ-ɚɦɢɞɨɮɟɧɨɥɹɬɧɵɯ ɥɢɝɚɧɞɨɜ [ 53,[82][83][84]. ɋɯɟɦɚ 8. ɨ-Ⱥɦɢɞɨɮɟɧɨɥɹɬɧɵɟ ɩɪɨɢɡɜɨɞɧɵɟ ɫɜɢɧɰɚ ɋɂɇɌȿɁ ɂ ɊȿȺɄɐɂɈɇɇȺə ɋɉɈɋɈȻɇɈɋɌɖ ȽȿɌȿɊɈɐɂɄɅɂɑȿɋɄɂɏ ɌəɀȿɅɕɏ ȺɇȺɅɈȽɈȼ ɄȺɊȻȿɇɈȼ ȼ ɧɚɫɬɨɹɳɟɦ ɨɛɡɨɪɟ ɦɵ ɧɟ ɛɭɞɟɦ ɩɨɞɪɨɛɧɨ ɨɫɬɚɧɚɜɥɢɜɚɬɶɫɹ ɧɚ ɬɚɤɨɦ ɨɛɲɢɪɧɨɦ ɧɚɩɪɚɜɥɟɧɢɢ, ɤɚɤ ɬɹɠɟɥɵɟ ɚɧɚɥɨɝɢ ɤɚɪɛɟɧɨɜ ɧɚ ɨɫɧɨɜɟ ɤɪɟɦɧɢɹ: ɷɬɚ ɨɛɥɚɫɬɶ ɩɨɞɪɨɛɧɨ ɨɛɫɭɠɞɚɟɬɫɹ ɜ ɰɟɥɨɦ ɪɹɞɟ ɧɟɞɚɜɧɢɯ ɨɛɡɨɪɨɜ, ɩɨɫɜɹɳɟɧɧɵɯ NHSi [85][86][87][88][89][90], ɦɨɧɨɚɧɢɨɧɧɵɦ ɧɟɝɟɬɟɪɨɰɢɤɥɢɱɟɫɤɢɦ ɦɟɬɚɥɥɟɧɚɦ [91][92][93][94][95][96][97] ɢ ɪɚɫɱɟɬɧɵɦ ɪɚɛɨɬɚɦ [ 21,[98][99][100]. ...
... ȼ ɩɭɛɥɢɤɚɰɢɹɯ ɨɩɢɫɚɧ ɰɟɥɵɣ ɪɹɞ ɩɪɢɦɟɪɨɜ ɬɚɤɢɯ ɤɚɬɚɥɢɡɚɬɨɪɨɜ ɞɥɹ ɩɨɥɢɦɟɪɢɡɚɰɢɢ ɥɚɤɬɢɞɚ, ɰɢɚɧɨɫɢɥɢɥɢɪɨɜɚɧɢɹ ɢɥɢ ɝɢɞɪɨɛɨɪɢɪɨɜɚɧɢɹ ɤɚɪɛɨɧɢɥɶɧɵɯ ɫɨɟɞɢɧɟɧɢɣ [ 155,189,190 ]. ɏɢɦɢɤɢ-ɫɢɧɬɟɬɢɤɢ ɜɫɟ ɱɚɳɟ ɩɟɪɟɤɥɸɱɚɸɬ ɫɜɨɢ ɢɧɬɟɪɟɫɵ ɨɬ ɬɨɤɫɢɱɧɵɯ ɢ ɞɨɪɨɝɨɫɬɨɹɳɢɯ ɤɚɬɚɥɢɡɚɬɨɪɨɜ ɧɚ ɨɫɧɨɜɟ ɩɟɪɟɯɨɞɧɵɯ ɦɟɬɚɥɥɨɜ ɧɚ ɛɨɥɟɟ ɷɤɨɧɨɦɢɱɧɵɟ, ɷɤɨɥɨɝɢɱɧɵɟ, ɥɟɝɤɨɞɨɫɬɭɩɧɵɟ ɢ ɪɚɫɩɪɨɫɬɪɚɧɟɧɧɵɟ ɩɪɨɦɨɭɬɟɪɵ ɪɟɚɤɰɢɣ. ɂɡɜɟɫɬɧɵ ɩɪɢɦɟɪɵ N-ɝɟɬɟɪɨɰɢɤɥɢɱɟɫɤɢɯ ɤɚɪɛɟɧɨɜ, ɞɟɣɫɬɜɭɸɳɢɯ ɢɫɤɥɸɱɢɬɟɥɶɧɨ ɤɚɤ ɨɪɝɚɧɨɤɚɬɚɥɢɡɚɬɨɪɵ ɢɥɢ ɞɨɩɨɥɧɹɸɳɢɯ ɤɨɨɪɞɢɧɢɪɭɸɳɭɸ ɫɮɟɪɭ ɤɚɬɚɥɢɡɚɬɨɪɨɜ ɧɚ ɨɫɧɨɜɟ ɩɟɪɟɯɨɞɧɵɯ ɦɟɬɚɥɥɨɜ ɜ ɤɚɱɟɫɬɜɟ ɜɫɩɨɦɨɝɚɬɟɥɶɧɨɝɨ ɥɢɝɚɧɞɚ [ 14,20,100,191 ]. ɉɪɢ ɷɬɨɦ ɝɪɚɧɢɰɵ ɤɚɬɚɥɢɬɢɱɟɫɤɢɯ ɜɨɡɦɨɠɧɨɫɬɟɣ ɬɹɠɟɥɵɯ ɝɟɬɟɪɨɰɢɤɥɢɱɟɫɤɢɯ ɬɟɬɪɚɥɢɥɟɧɨɜɝɟɪɦɢɥɟɧɨɜ ɢ ɫɬɚɧɧɢɥɟɧɨɜ -ɥɢɲɶ ɧɚ ɧɚɱɚɥɶɧɨɣ ɫɬɚɞɢɢ ɚɤɬɢɜɧɨɝɨ ɢɡɭɱɟɧɢɹ. ...
... The halogen bond (XB) [52][53][54][55][56][57] is one of a family of noncovalent bonds, including also chalcogen, pnicogen, and tetrel bonds, [58][59][60][61][62][63][64][65] in which the bridging proton of the HB is replaced by any of a large group of other elements. Because most of the halogen atoms are more electronegative than H, one cannot assign an overall positive charge to X as one can for H. Nonetheless, there is a high degree of anisotropy of electron density around X, which leads in turn to a positive region of the electrostatic potential that is focused along the extension of the A-X bond. ...
The halogen bond formed by a series of Lewis acids TF3X (T = C, Si, Ge, Sn, Pb; X = Cl, Br, I) with NH3 is studied by quantum chemical calculations. The interaction energy is closely mimicked by the depth of the σ-hole on the X atom as well as the full electrostatic energy. There is a first trend by which the hole is deepened if the T atom to which X is attached becomes more electron-withdrawing: C > Si > Ge > Sn > Pb. On the other hand, larger more polarizable T atoms are better able to transmit the electron-withdrawing power of the F substituents. The combination of these two opposing factors leaves PbF3X forming the strongest XBs, followed by CF3X, with SiF3X engaging in the weakest bonds. The charge transfer from the NH3 lone pair into the σ*(TX) antibonding orbital tends to elongate the covalent TX bond, and this force is largest for the heavier X and T atoms. On the other hand, the contraction of this bond deepens the σ-hole at the X atom, which would enhance both the electrostatic component and the full interaction energy. This bond-shortening effect is greatest for the lighter X atoms. The combination of these two opposing forces leaves the T-X bond contracting for X = Cl and Br, but lengthening for I.
... The general framework of the PnB is repeated in a number of very similar noncovalent bonds, known as halogen, chalcogen, tetrel, and triel bonds [1][2][3][4][5][6][7][8][9][10], depending upon the family of elements from which the bridging atom is drawn. ...
Bonding within the AsF3 crystal is analyzed via quantum chemical methods so as to identify and quantify the pnicogen bonds that are present. The structure of a finite crystal segment containing nine molecules is compared with that of a fully optimized cluster of the same size. The geometries are qualitatively different, with a much larger binding energy within the optimized nonamer. Although the total interaction energy of a central unit with the remaining peripheral molecules is comparable for the two structures, the binding of the peripherals with one another is far larger in the optimized cluster. This distinction of much stronger total binding within the optimized cluster is not limited to the nonamer but repeats itself for smaller aggregates as well. The average binding energy of the cluster rises quickly with size, asymptotically approaching a value nearly triple that of the dimer.
The five-membered heteroaromatic thiazole molecule contains a number of electron-rich regions that could attract an electrophile, namely the N and S lone pairs that lie in the molecular plane, and π-system areas above the plane. The possibility of each of these sites engaging in a tetrel bond (TB) with CF4 and SiF4, as well as geometries that encompass a CH⋯F H-bond, was explored via DFT calculations. There are a number of minima that occur in the pairing of thiazole with CF4 that are very close in energy, but these complexes are weakly bound by less than 2 kcal mol-1 and the presence of a true TB is questionable. The inclusion of zero-point vibrational energies alters the energetic ordering, which is further modified when entropic effects are added. The preferred geometry would thus be sensitive to the temperature of an experiment. Replacement of CF4 by SiF4 leaves intact most of the configurations, and their tight energetic clustering, the ordering of which is again altered as the temperature rises. But there is one exception in that by far the most tightly bound complex involves a strong Si⋯N TB between SiF4 and the lone pair of the thiazole N, with an interaction energy of 30 kcal mol-1. Even accounting for its high deformation energy and entropic considerations, this structure remains as clearly the most stable at any temperature.
