Weak attractive interactions between closed shell metal ions have been increasingly studied in the last few years and are generally designated as metallophilic interactions. They are best evidenced in the solid state where structural data obtained by X-ray diffraction provide precise information about the distance between the metals involved. The strength of such metal-metal interactions has been compared to that of hydrogen bonding (ca. 7-11 kcal mol(-1)) and is clearly sufficient to bring about novel bonding and structural features and confer interesting physical properties such as luminescence, polychromism, magnetism or one-dimensional electrical conductivity. The Cu(I)-Cu(I), Ag(I)-Ag(I) and Au(I)-Au(I) interactions have been increasingly observed and the latter have certainly been the most studied. Early qualitative analyses of the aurophilic attraction focused on Au-Au bonding originating from 6s, 6p and 5d orbital mixing. Numerous theoretical studies on metallophilic interactions continue to be carried out at various levels of sophistication which take into account relativistic and correlation effects to describe these van der Waals-type interactions. In this critical review, we would like to focus on the synthesis and structures of heterometallic clusters of the transition metals in which intra- rather than intermolecular d(10)-d(10) interactions are at work, in order to limit the role of packing effects. We wish to provide the reader with a comparative overview of the metal core structures resulting from or favoring metallophilic interactions but do not intend to provide a comprehensive coverage of the literature. We will first examine heterometallic clusters displaying homometallic and then heterometallic d(10)-d(10) interactions. Although the focus of this review is on d(10)-d(10) interactions involving metals from the group 11, we shall also briefly examine for comparison some complexes displaying intramolecular d(10)-d(10) interactions involving metals from other groups (188 references).

Gilded rafts: Oligomeric 2D raft clusters {M[m]}n (M=Cu, n=3; M=Ag or Au, n=4; see picture) with the same bridging metalloligand [m]={CpMo(CO)3} were prepared and structurally characterized. The ν2‐triangular (M=Cu) or ν2‐square (M=Ag, Au) structures of their metal–metal‐bonded cores allow comparative evaluation of the d10⋅⋅⋅d10 interactions, and theoretical calculations point to a favorable contribution of diagonal Au⋅⋅⋅Au or Ag⋅⋅⋅Ag interactions.