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Chemistry. 2013 Sep 9;19(37):12264-71. doi: 10.1002/chem.201302152. Epub 2013 Aug 9.

A unique Au-Ag-Au triangular motif in a trimetallic halonium dication: silver incorporation in a gold(I) catalyst.

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  • 1Chemistry Department, Wake Forest University, Salem Hall, Box 7486 (USA), Fax: (+1) 336-758-4656.


As a result of explorations into the solution chemistry of silver/gold mixtures, a unique diphosphine trimetallic chloronium dication was discovered that incorporates silver-arene chelation and a triangular mixed gold/silver core in the solid state. Notably, it was isolated from a Celite prefiltered solution initially thought to be silver-free. The crystal structure also incorporates the coordination to silver of one fluorine atom of one SbF6(-) counterion. The structure was compared to two new, but well-precedented, phosphine digold chloride cations. DFT calculations supported significant silver-halide and silver-arene interactions in the mixed gold/silver complex and metallophilic interactions in all three complexes. Comparison of computed data revealed that the ωB97X-D functional, which has a long-range corrected hybrid with atom-atom dispersion corrections, gave a better fit to the experimental data compared with the PBE0 functional, which has previously failed to capture aurophilic interactions. Preliminary studies support the presence of the mixed gold/silver structure in solution.

Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


aurophilicity; cluster compounds; gold; pi interactions; silver

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