On the ability of pnicogen atoms to engage in both σ and π-hole complexes. Heterodimers of ZF2C6H5 (Z = P, As, Sb, Bi) and NH3

Zierkiewicz, Wiktor; Michalczyk, Mariusz; Wysokiński, Rafał; Scheiner, Steve

doi:10.1007/s00894-019-4031-6

Cited by 31 publications

(21 citation statements)

References 106 publications

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“…The concept of a σ-hole was introduced by Politzer et al [2][3][4][5] to describe regions of positive potential along the vector of a covalent bond. It was latter extended to other situations, for example, the π-hole [6][7][8][9][10][11] (positive electrostatic potential perpendicular to an atom of a molecular framework) and lone pair hole (similar to σ-hole but along the atom-lone pair direction) [12][13][14]. The maximum value of the molecular electrostatic potential within a given molecular density isosurface surface, V S,max , has also been classified based on the nature of the orbitals (s-, p-and d-orbitals) and it is associated with the corresponding deficiencies (σ s -, σ p -and σ d -holes) [15].…”

Section: Introductionmentioning

confidence: 99%

Regium Bonds between Silver(I) Pyrazolates Dinuclear Complexes and Lewis Bases (N2, OH2, NCH, SH2, NH3, PH3, CO and CNH)

et al. 2020

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A theoretical study and Cambridge Structural Database (CSD) search of dinuclear Ag(I) pyrazolates interactions with Lewis bases were carried out and the effect of the substituents and ligands on the structure and on the aromaticity were analyzed. A relationship between the intramolecular Ag–Ag distance and stability was found in the unsubstituted system, which indicates a destabilization at longer distances compensated by ligands upon complexation. It was also observed that the asymmetrical interaction with phosphines as ligands increases the Ag–Ag distance. This increase is dramatically higher when two simultaneous PH3 ligands are taken into account. The calculated 109Ag chemical shielding shows variation up to 1200 ppm due to the complexation. Calculations showed that six-membered rings possessed non-aromatic character while pyrazole rings do not change their aromatic character significantly upon complexation.

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Section: Introductionmentioning

confidence: 99%

Regium Bonds between Silver(I) Pyrazolates Dinuclear Complexes and Lewis Bases (N2, OH2, NCH, SH2, NH3, PH3, CO and CNH)

et al. 2020

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“…Recent years have witnessed a growing recognition of a range of newly rediscovered noncovalent bonds. Similarly to their closely related H-bond cousin, this class of bonds [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25] are derived from a primary electrostatic attraction, supplemented by substantial amounts of charge transfer, polarization, and dispersion ingredients. In addition to their occurrence in small-model dimers, these sorts of interactions are a major factor in the structure and function of much larger supramolecular systems [26,27,28,29,30,31,32,33,34,35].…”

Section: Introductionmentioning

confidence: 99%

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

Scheiner

2019

Molecules

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Complexes were formed pairing FX, FHY, FH2Z, and FH3T (X = Cl, Br, I; Y = S, Se, Te; Z = P, As, Sb; T = Si, Ge, Sn) with NH3 in order to form an A⋯N noncovalent bond, where A refers to the central atom. Geometries, energetics, atomic charges, and spectroscopic characteristics of these complexes were evaluated via DFT calculations. In all cases, the A–F bond, which is located opposite the base and is responsible for the σ-hole on the A atom, elongates and its stretching frequency undergoes a shift to the red. This shift varies from 42 to 175 cm−1 and is largest for the halogen bonds, followed by chalcogen, tetrel, and then pnicogen. The shift also decreases as the central A atom is enlarged. The NMR chemical shielding of the A atom is increased while that of the F and electron donor N atom are lowered. Unlike the IR frequency shifts, it is the third-row A atoms that undergo the largest change in NMR shielding. The change in shielding of A is highly variable, ranging from negligible for FSnH3 all the way up to 1675 ppm for FBr, while those of the F atom lie in the 55–422 ppm range. Although smaller in magnitude, the changes in the N shielding are still easily detectable, between 7 and 27 ppm.

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“…Depending upon the column of the periodic table from which this bridging atom is drawn, the resulting noncovalent bond with a nucleophile is designated as a halogen (XB), chalcogen (YB), pnicogen (ZB), or tetrel (TB) bond. Like the HB, this class of bonds [10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36] are similarly derived from a primary electrostatic attraction, supplemented by substantial amounts of charge transfer, polarization, and dispersion components.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Studies of IR and NMR Spectral Changes Induced by Sigma-Hole Hydrogen, Halogen, Chalcogen, Pnicogen, and Tetrel Bonds in a Model Protein Environment

et al. 2019

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Various types of σ-hole bond complexes were formed with FX, HFY, H2FZ, and H3FT (X = Cl, Br, I; Y = S, Se, Te; Z = P, As, Sb; T = Si, Ge, Sn) as Lewis acid. In order to examine their interactions with a protein, N-methylacetamide (NMA), a model of the peptide linkage was used as the base. These noncovalent bonds were compared by computational means with H-bonds formed by NMA with XH molecules (X = F, Cl, Br, I). In all cases, the A–F bond, which lies opposite the base and is responsible for the σ-hole on the A atom (A refers to the bridging atom), elongates and its stretching frequency undergoes a shift to the red with a band intensification, much as what occurs for the X–H bond in a H-bond (HB). Unlike the NMR shielding decrease seen in the bridging proton of a H-bond, the shielding of the bridging A atom is increased. The spectroscopic changes within NMA are similar for H-bonds and the other noncovalent bonds. The C=O bond of the amide is lengthened and its stretching frequency red-shifted and intensified. The amide II band shifts to higher frequency and undergoes a small band weakening. The NMR shielding of the O atom directly involved in the bond rises, whereas the C and N atoms both undergo a shielding decrease. The frequency shifts of the amide I and II bands of the base as well as the shielding changes of the three pertinent NMA atoms correlate well with the strength of the noncovalent bond.

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On the ability of pnicogen atoms to engage in both σ and π-hole complexes. Heterodimers of ZF2C6H5 (Z = P, As, Sb, Bi) and NH3

Cited by 31 publications

References 106 publications

Regium Bonds between Silver(I) Pyrazolates Dinuclear Complexes and Lewis Bases (N2, OH2, NCH, SH2, NH3, PH3, CO and CNH)

Regium Bonds between Silver(I) Pyrazolates Dinuclear Complexes and Lewis Bases (N2, OH2, NCH, SH2, NH3, PH3, CO and CNH)

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

Theoretical Studies of IR and NMR Spectral Changes Induced by Sigma-Hole Hydrogen, Halogen, Chalcogen, Pnicogen, and Tetrel Bonds in a Model Protein Environment

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