A novel concept for the synthesis of multiply doped gold clusters [(M@Au(n)M'(m))L(k)](q+).

Heterometal-doped gold clusters are poorly accessible through wet-chemical approaches and main-group-metal- or early-transition-metal-doped gold clusters are rare. Compounds [M(AuPMe3 )11 (AuCl)](3+) (M=Pt, Pd, Ni) (1-3), [Ni(AuPPh3 )(8-2n) (AuCl)3 (AlCp*)n ] (n=1, 2) (4, 5), and [Mo(AuPMe3 )8 (GaCl2 )3 (GaCl)](+) (6) were selectively obtained by the transmetalation of [M(M'Cp*)n ] (M=Mo, E=Ga, n=6; M=Pt, Pd, Ni, M'=Ga, Al, n=4) with [ClAuPR3 ] (R=Me, Ph) and characterized by single-crystal X-ray diffraction and ESI mass spectrometry. DFT calculations were used to analyze the bonding situation. The transmetalation proved to be a powerful tool for the synthesis of heterometal-doped gold clusters with a design rule based on the 18 valence electron count for the central metal atom M and in agreement with the unified superatom concept based on the jellium model.