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An asymmetric bipy/NHC ligand L has been used to construct Au/Au, Au/Ag and Au/Cu bimetallic complexes through prior coordination of the NHC to Au(I) and subsequent introduction of the second group 11 metal ion at the bipy donor of the hybrid ligand. The complex [Au(κC-L)2]BF4, 1, has been used as the precursor for the formation of [AuAg(κ-CAu,κ2-N,N′Ag-1)2](BF4)2, 2a, [AuCu(κ-CAu,κ2-N,N′Cu-1)2](BF4)2, 2b and [AuAu′(κ-CAu/Au′,κ1-NAu/Au′-1)2](BF4)2, 3.
