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Enhanced Metallophilicity in Metal–Carbene Systems: Stronger Character of Aurophilic Interactions in Solution
Author(s) -
Vellé Alba,
RodríguezSantiago Luis,
Sodupe Mariona,
Sanz Miguel Pablo J.
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201904507
Subject(s) - van der waals force , cationic polymerization , carbene , ion , character (mathematics) , crystallography , chemical physics , chemistry , metal , quantum chemical , rigidity (electromagnetism) , intermolecular force , materials science , molecule , physics , quantum mechanics , polymer chemistry , organic chemistry , catalysis , geometry , mathematics
Metallophilicity is an essential concept that builds upon the attraction between closed shell metal ions. We report on the [M 2 (bisNHC) 2 ] 2+ (M=Au I , Ag I ; NHC= N ‐heterocyclic carbene) systems, which display almost identical features in the solid state. However, in solution the Au 2 cation exhibits a significantly higher degree of rigidity owed to the stronger character of the aurophilic interactions. Both Au 2 and Ag 2 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.