Modulating the intrinsic reactivity of molecules through non-covalent interactions

Montero‐Campillo, M. Merced; Brea, Oriana; Mó, Otília; Alkorta, Ibón; Elguero, José; Yáñez, Manuel

doi:10.1039/c8cp06908e

Cited by 17 publications

(9 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Cooperativity has been considered as the characteristic feature of secondary interactions in the literature. [6,[8][9][10][60][61][62][63][64][65][66][67] That is, the intermolecular distance decreases as the intermolecular binding energy increases when the number of molecules involved in the complex increases.…”

Section: Cooperativity Induced By Polarizationmentioning

confidence: 99%

Beryllium bonding: insights from the σ- and π-hole analysis

Alikhani

2020

J Mol Model

View full text Add to dashboard Cite

Beryllium bonding is actually a subclass of secondary bonding. Similar to the case of halogen bonding, the σ-and π-holes on the Be atom of the monomers give in zeroth-approximation the direction of electrophilic attack favorable to the formation of beryllium bonds. The nature of beryllium bonding is purely electrostatic so that the SAPT energy decomposition perfectly explains the relevance of the polarization-and dispersion-contribution on the formation of the beryllium bond.

show abstract

Section: Cooperativity Induced By Polarizationmentioning

confidence: 99%

Beryllium bonding: insights from the σ- and π-hole analysis

Alikhani

2020

J Mol Model

View full text Add to dashboard Cite

show abstract

“…In each of the chalcogen, pnicogen, tetrel, and triel bonds, an atom of that same particular family of the periodic table replaces the bridging proton of the H-bond. − Among these interactions, the halogen bond (XB) is arguably the one that has been acknowledged for the longest time − and has engendered the greatest amount of scrutiny. Extensive study has demonstrated that the XB owes its stability to several factors. − In the first place, the electron-density cloud surrounding the X atom is quite anisotropic; while the overall charge on the X atom is partially negative, there is a pocket of positive potential that lies along the extension of the covalent C–X bond, which is commonly referred to as a σ-hole. This positive region attracts the negative potential of an approaching nucleophile, for example, its lone pair, leading to a Coulombic attraction.…”

Section: Introductionmentioning

confidence: 99%

Proximity Effects of Substituents on Halogen Bond Strength

Lapp

Scheiner

2021

J. Phys. Chem. A

View full text Add to dashboard Cite

It is well known that the presence of an electron-withdrawing substituent (EWS) placed near the halogen (X) atom on a Lewis acid molecule amplifies the ability of this unit to engage in a halogen bond with a base. Quantum calculations are applied to examine how quickly these effects fade as the EWS is moved further and further from the X atom. Conjugated alkene and alkyne chains of varying lengths with a terminal C−I first facilitate analysis as to how the number of these multiple bonds affects the strength of CI••N XB to NH 3 . Then, electron-withdrawing F and CN substituents are placed on the opposite end of the chain, and their effects on the XB properties are monitored as a function of their distance from I. These same EWSs are added to the ortho, meta, and para positions of aromatic iodobenzene. It is found that the XB grows in strength as more triple bonds are added to the alkyne, but there is little change caused by elongating an alkene. The cyano group has a much stronger effect than does F. While F strengthens the XB, its effects are quickly attenuated as it is moved further from I. The consequences of CN substitution are stronger and extend over a longer distance. Placement of an EWS on the phenyl ring diminishes with distance: o > m > p, and the effects of disubstitution are nearly additive. These trends apply not only to energetics but also to geometries, properties of the wave function, σ-hole depth, and NMR shielding.

show abstract

“…11,12 The formation of alkaline-earth bonds results in a significant electron density redistribution of the Lewis base interacting with the Be or Mg derivative, modifying the Lewis base reactivity. 13,14 The consequence is that the formation of alkaline-earth bonds modulates the strength of other non-covalent interactions in which the Lewis base participates, such as hydrogen bonds, 15,16 halogen bonds, [17][18][19] or tetrel bonds. 20,21 They also contribute to create σ-holes, 22 or to spontaneously produce radicals.…”

Section: Introductionmentioning

confidence: 99%

Significant bonding rearrangements triggered by Mg4 clusters

Vos

Corral

Montero‐Campillo

et al. 2021

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

Among new nanostructures with exciting reactivity features, Mg4 clusters present a promising catalytic behavior. The structure, stability and bonding of the complexes formed by the interaction of Mg4 clusters and first row Lewis bases, namely ammonia, water and hydrogen fluoride, have been investigated through the use of high-level G4 single-reference and CASPT2 multireference formalisms. The adducts formed reflect the high electrophilicity of the Mg4 cluster through holes in the neighborhood of each metallic center. After the adducts formation, the metallic bonding of the Mg4 moiety is not significantly altered so the hydrogen shifts from the Lewis base toward the Mg atoms lead to new local minima with enhanced stability. For the particular case of ammonia and water, the global minima obtained when all the hydrogens of the Lewis base are shifted to the Mg4 moiety have in common a very stable scaffold with a N or O center covalently tetracoordinated to the four Mg atoms, so the initial bonding arrangements of both reactants have completely disappeared.

show abstract

Modulating the intrinsic reactivity of molecules through non-covalent interactions

Abstract: Non-covalent interactions as tools for modifying molecular properties.

Cited by 17 publications

References 54 publications

Beryllium bonding: insights from the σ- and π-hole analysis

Beryllium bonding: insights from the σ- and π-hole analysis

Proximity Effects of Substituents on Halogen Bond Strength

Significant bonding rearrangements triggered by Mg4 clusters

Contact Info

Product

Resources

About