Weak Intramolecular Bonding Relationships: The Conformation‐Determining Attractive Interaction between Gold(I) Centers

Abstract

AuAu distances of only 3.000 Å in the complex 2 are convincing evidence for the existence of attractive interactions between Au1 centers. 2 is formed from 1 and [(CO)AuCl] with rotation of a CP bond. 1, Ph instead of Me, is sterically too strongly hindered for this reaction.

The aurophilicity phenomenon: A decade of experimental findings, theoretical concepts and emerging applications

“…If the gold atoms are further apart and attached to a flexible molecular skeleton, their interaction leads to the adoption of unusual conformations which allow the mutual approach to reach the optimum equilibrium distance (ca 3 Å) (9). This effect was found in a large number of molecules where two or more X-Au-Y units are, for example, at the ends of hydrocarbon chains: a folding into the cis-conformations is observed which brings the ends into close proximity, and the ends are thus fixed in a non-standard configuration by Au-Au bonding (2).…”

“…Some molecules of this type were thus found to adopt unusual conformations, in which the gold atoms can become nearest neighbours (9). The gain in stability through these non-classical interactions was obviously also the reason for unexpected multiauration processes which lead to a gathering of gold atoms at certain functions of a substrate (5, 10).…”

Structural characterization of dinuclear gold(I) diphosphine complexes with anion-triggered luminescence

“…Theoretical studies have shown that the aurophilic interaction is the result of correlation effects that are enhanced by relativistic effects [7,8]. The aurophilic interactions between the closed-shell Au(I) centres are important in determining the solid state structures of many gold(I) compounds and contribute to the chemical and physical properties of these complexes [1][2][3][4][9][10][11][12][13]. The distance between two interacting gold atoms in compounds showing aurophilic interactions is less than 3.6 Å.…”

Polymorphism and luminescent behavior of linear, two-coordinate gold(i) complexes

“…Au interaction, have shown that the strength of the attractive aurophilic interaction is comparable to that of hydrogen-bonding: ca. 7-11 kcal/mol (20,21). In cases where multiple Au ...…”