The borderless world of chemical bonding across the van der Waals crust and the valence region

Abstract

The definition of the Van der Waals crust as the spherical section comprised between the atomic radius and the Van der Waals radius of an element is discussed and a...

Azido-mediated intermolecular interactions of transition metal complexes

“…5(a)), as noted earlier by us for other intermolecular interactions. 45 In this case, the correlation is somewhat poor because not only the interpenetration of the VdW crusts vary from one molecule to another, but there are also important topological differences in the contacts. The clearest conclusion that can be drawn from the analysis of the results of the EDA analysis of several models of azide⋯azide interactions is that its attractive nature is due to the London dispersion forces, which are quantitatively predominant, between 4 and 13-fold times stronger than the orbital term, although in the case of 5a the dispersion term is not enough by itself to counteract the Pauli repulsion, and the small electrostatic and orbital contributions (−0.14 and and −0.23 kcal mol −1 , respectively) become crucial to make the whole interaction attractive.…”

“…Interestingly, all structures with a torsion angle τ of 90° ( 1b–9b ) exhibit in addition short N⋯Hg contacts that cover a wide range of penetration indices, from small negative values (distances slightly longer than the VdW sum) up to positive values as high as 32%, comparable to those found for weak hydrogen bonds. 45…”

Adducts of a Triangular Copper(I) Pyrazolate with Thiophenic Compounds Featuring Short Cu(I)–S Contacts

“…A negative RCD% may imply a negligible or very weak interaction. A similar parameter, called the penetration index, has been defined in a recent publication and extensively applied in the study of two interacting atoms in a wide variety of covalent, polar, coordinative or noncovalent bonding situations …”

“…A similar parameter, called the penetration index, has been defined in a recent publication and extensively applied in the study of two interacting atoms in a wide variety of covalent, polar, coordinative or noncovalent bonding situations. 19 Table 1 lists 21,22 it is still amazing to observe the severe distortion of Cu 3 pz 3 upon binding to thiophenic compounds because the latter are usually considered a kind of weak ligand. 23 It is informative to compare the Cu−S distances of Cu 3 pz 3 -DBT/DMDBT adducts with those of the Ag 3 pz 3 /[Cu-(denpz)] 3 -DBT/DMDBT adducts.…”

Chirality Generated by Hindered Rotations in Platinum(II)‐Pyridine Complexes

“…[20] During the preparation of this manuscript Echeverrìa and Alvarez published a paper where several types of bonds were investigated and commented. [21] The authors analyzed the interpenetration between spheres of electron density (defined by van der Waals and covalent radii): when two atoms are involved in a bonding interaction, the outermost spheres of electron density interpenetrate to a greater or lesser extent depending on the strength of the interaction.…”