A Novel Concept for the Synthesis of Multiply Doped Gold Clusters (M@Au_nM_m)L_k~(q+)

摘要

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)_n(AuCl)~(3+) (M = Pt, Pd, Ni) (1-3), Ni(AuPPh3)_(8-2n)(AuCl)3(AlCp)_n (n = l, 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 ClAuPRJ (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.