A Unique Au–Ag–Au Triangular Motif in a Trimetallic Halonium Dication: Silver Incorporation in a Gold(I) Catalyst |
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Authors: | Yuyang Zhu Dr Cynthia S Day Lin Zhang Katarina J Hauser Prof Amanda C Jones |
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Institution: | Chemistry Department, Wake Forest University, Salem Hall, Box 7486 (USA), Fax: (+1)?336‐758‐4656 |
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Abstract: | 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. |
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Keywords: | aurophilicity cluster compounds gold pi interactions silver |
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