Metallation of a gold(i) metalloligand with P,C-bridging phosphinoferrocenyl groups enables the construction of defined multimetallic arrays†‡
Abstract
The reactions of the gold(I) metalloligand [Au2{μ(P,C)-Ph2Pfc}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.