Metallation of a gold(I) metalloligand with P,C-bridging phosphinoferrocenyl groups enables the construction of defined multimetallic arrays.

The reactions of the gold(I) metalloligand [Au 2 {μ(P,C)-Ph 2 Pfc} 2 ], where fc stands for ferrocene-1,1'-diyl, with bare or ligand-stabilised group 11 metal ions open access to diverse oligometallic clusters stabilised by Au-Au, Au-Ag and Au-Cu interactions. These capping reactions and the unique structures of the products stem from unparalleled properties of the bridging ferrocene groups, namely their structural flexibility and electron-rich nature, which enable accommodating the capping moieties and supporting ligands and facilitate electrophilic metalation, respectively. While the Au + and Ag + ions behave similarly, capping reactions with Cu + proceed differently, with an accentuated role of the counter ions and other ligands in the system. Such behaviour reflects the relative strengths of the Au-M metallophilic interaction (M = Au, Ag and Cu), among which the Au-Cu interactions are the weakest, as confirmed by DFT calculations.