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A Unique Au–Ag–Au Triangular Motif in a Trimetallic Halonium Dication: Silver Incorporation in a Gold(I) Catalyst
Author(s) -
Zhu Yuyang,
Day Cynthia S.,
Zhang Lin,
Hauser Katarina J.,
Jones Amanda C.
Publication year - 2013
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.201302152
Subject(s) - dication , counterion , silver salts , chemistry , phosphine , silver halide , crystallography , atom (system on chip) , halide , catalysis , inorganic chemistry , ion , organic chemistry , layer (electronics) , computer science , embedded system
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 SbF 6 − 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.