Enhanced metallophilicity in metal–carbene systems: Stronger character of aurophilic interactions in solution

Metallophilicity is an essential concept that builds upon the attraction between closed shell metal ions. We report on the [M2(bisNHC)2]2+ (M=AuI, AgI; NHC=N‐heterocyclic carbene) systems, which display almost identical features in the solid state. However, in solution the Au2 cation exhibits a significantly higher degree of rigidity owed to the stronger character of the aurophilic interactions. Both Au2 and Ag2 cationic constructs are able to accommodate Ag+ ions via M–M interactions, despite their inherent Coulombic repulsion. When electrostatic repulsion between host and guest is partially diminished, M–M distances are substantially shortened. Quantum chemical calculations estimate intermetallic bond orders up to 0.2. Although at the limit of (or beyond) the van der Waals radii, metallophilic interactions are responsible for their behavior in solution.Financial support from the University of Zaragoza (UZ2018‐CIE‐06), the Aragón Government (E42_17R, and A.V. predoctoral fellow), the MINECO (CTQ2017‐89132‐P) and the Generalitat de Catalunya (2017SGR1323) is kindly acknowledged.Peer reviewe