Enhanced metallophilicity in metal-carbene systems : stronger character of aurophilic interactions in solution
Vellé, Alba (Universidad de Zaragoza. Departamento de Química Inorgánica)
Rodríguez Santiago, Luis (Universitat Autònoma de Barcelona. Departament de Química)
Sodupe Roure, Mariona (Universitat Autònoma de Barcelona. Departament de Química)
Sanz Miguel, Pablo J. (Universidad de Zaragoza. Departamento de Química Inorgánica)

Data:	2020
Resum:	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 solid state. However, in solution the Au2 cation exhibits a significant 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.
Ajuts:	Agencia Estatal de Investigación CTQ2017-89132-P Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-1323
Drets:	Tots els drets reservats.
Llengua:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Matèria:	Argentophilicity ; Aurophilicity ; Host-guest systems ; Metal-metal interactions ; Van der Waals radii
Publicat a:	Chemistry, Vol. 26, issue 5 (Jan. 2022) , p. 997-1002, ISSN 1521-3765

DOI: 10.1002/chem.201904507

Postprint 7 p, 1.4 MB

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