Anorganische Chemie II - Organometallics & Materials, Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, 44801 Bochum (Germany).
Angew Chem Int Ed Engl. 2014 Apr 22;53(17):4327-31. doi: 10.1002/anie.201310436. Epub 2014 Apr 2.
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) (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.
杂金属掺杂的金团簇难以通过湿化学方法获得，而主族金属或早期过渡金属掺杂的金团簇则很少见。通过[M(AuPMe3 )11 (AuCl)]3+（M=Pt、Pd、Ni）（1-3）、[Ni(AuPPh3 )(8-2n) (AuCl)3 (AlCp*)n ]（n=1、2）（4、5）和[Mo(AuPMe3 )8 (GaCl2 )3 (GaCl)]+（6）的反金属转移反应，选择性地得到了[M(M'Cp*)n ]（M=Mo、E=Ga、n=6；M=Pt、Pd、Ni、M'=Ga、Al、n=4）与[ClAuPR3 ]（R=Me、Ph）的反应产物，并通过单晶 X 射线衍射和 ESI 质谱进行了表征。DFT 计算用于分析成键情况。反金属转移反应被证明是一种合成杂金属掺杂金团簇的有效工具，其设计规则基于中心金属原子 M 的 18 价电子计数，并与基于等电子模型的统一超原子概念一致。
