The Nature of Metal–Metal Interactions in Dimeric Hydrides and Halides of Group 11 Elements in the Light of High Level Relativistic Calculations

Abstract

The titular calculations show that charges at metal atoms M are apparently the main factor governing the nature of M⋅⋅⋅M interactions in two-nuclear coinage-metal complexes, and there are certain critical values of positive charges on M atoms, on exceeding which the pair-wise M⋅⋅⋅M interactions and/or the binding between M atoms in such complexes become repulsive despite negative formation energies of such complexes, short M-M internuclear distances, and the existence of a bond critical point (BCP) between M atoms.

Structural Diversity and Argentophilic Interactions in Small Phosphine Silver(I) Thiolate Clusters

“…u.). Likewise aurophilic contacts, it is expected that electron rich centers form stronger metallophilic interactions [64] . However, geometry plays a crucial role in the case of silver and thus, the less electron rich but linear centers rather than the electron rich centers of higher coordination number, form the strongest Ag⋅⋅⋅Ag interactions among the compounds presented herein.…”

Directing the Crystal Packing in Triphenylphosphine Gold(I) Thiolates by Ligand Fluorination

“…As recently stated by Dem’yanov et al, electron-rich gold centers tend to form relatively strong Au···Au contacts, but the relation between charge-density and the energetics of aurophilic interactions is not straightforward. The system with the largest DI­(Au···Au), and correspondingly the stronger interaction, is the dimer of the difluorinated compound 4 .…”

“…36 For example, electron-withdrawing substituents which decrease the electron density of Au centers weaken the gold−gold contacts. 38 The study of systems wherein the Au••• Au interactions are disfavored or overwhelmed by other synthons could underestimate the real significance of these interactions. 39 In contrast, the analyses of systems in which the Au•••Au contacts are favored indicate that they are as strong as other archetypical supramolecular interactions such as πstacking and hydrogen bonds.…”

“…Such modifications can be exploited in the control of aurophilic aggregates . For example, electron-withdrawing substituents which decrease the electron density of Au centers weaken the gold–gold contacts . The study of systems wherein the Au···Au interactions are disfavored or overwhelmed by other synthons could underestimate the real significance of these interactions .…”

Is there a Covalent Au(I)–Au(I) Bond in the trans-(AuX)2 (X = F, Cl, Br, I) Structure? A Post-Hartree–Fock and Density Functional Theory Study

“…59 In the current literature on metallophilic interactions, an interesting (MX) 2 (M = Cu, Ag, Au; X = F, Cl, Br, I, NH 2 ) complex with C 2h (trans), C 2v , and D 2h conformation has emerged. 61,62 In particular, models based on the trans-(C 2h ) geometry have called our attention because they show shorter metal−metal distances than those described by metallophilic interactions both experimentally and theoretically. However, the magnitudes of the interaction energies are closer to weak van der Waals interactions.…”