The reactions of the cationic transition metal acetonitrile complexes [M(CH3CN)n]m+ (m = 2: M = Fe, Co and m = 1: M = Cu, Ag) with GaCp* were investigated. The reaction of [Fe(CH3CN)6][BArF]2 (BAr(F) = [B{C6H3(CF3)2}4) with GaCp* leads to [Cp*Fe(GaCp*)3][BAr(F)] (1) via a redox neutral Cp* transfer and [Ga2Cp*][BAr(F)] as a by-product while the formation of [Cp*Co(GaCp*)3][BAr(F)]2 (2) from [Co(CH3CN)6][BAr(F)]2 is accompanied by oxidation of Co(II) to Co(III) with GaCp* as the oxidant. The reactions of [Cu(CH3CN)4][BAr(F)] and Ag[BPh4] with GaCp* lead to the formation of the homoleptic compounds [Cu(GaCp*)4][BAr(F)] (4) and [Ag(GaCp*)4][BPh4] (5), while treatment of Ag[CF3SO3] with GaCp* leads to the dimeric complex [Ag2(GaCp*)3(micro-GaCp*)2][CF3SO3]2 (6). All compounds were characterized by NMR spectroscopy, single crystal X-ray diffraction and elemental analysis.

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.

Palladium(II) complexes of bidentate cycloimidate ligand systems with a triarylmethyl moiety exhibit exceptional downfield shifts in proton NMR spectra due to rare anagostic interactions.

Heterometalldotierte Goldcluster sind durch nasschemische Synthese schwer zugänglich, und mit Hauptgruppenmetallen oder frühen Übergangsmetallen dotierte Cluster sind rar. Die Verbindungen [M(AuPMe 3 ) 11 (AuCl)] 3+ (M = Pt, Pd, Ni) (1-3), [Ni(AuPPh 3 ) (8-2n) (AuCl) 3 (AlCp*) n ] (n = 1, 2) (4, 5) und [Mo(AuPMe 3 ) 8 (GaCl 2 ) 3 (GaCl)] + (6) wurden selektiv durch Transmetallierung von [M(M'Cp*) n ] (M = Mo, E = Ga, n = 6; M = Pt, Pd, Ni, M' = Ga, Al; n = 4) mit [ClAuPR 3 ] (R = Me, Ph) hergestellt und mit Einkristallrçntgenbeugung sowie ESI-MS charakterisiert. Mithilfe von DFT-Rechnungen wurden die Bindungsverhältnisse analysiert. Die Transmetallierung ist eine wirkungsvolle Syntheseroute hin zu heterometalldotierten Goldclustern, deren Aufbau der 18-Valenzelektronenregel für das Zentralmetallatom gehorcht und die mit dem Superatomkonzept auf Grundlage des Jellium-Modells übereinstimmen.[**] A.P. dankt für ein Stipendium des FCI sowie für finanzielle Unterstützung durch die Research School der Ruhr-Universität und den DAAD.Hintergrundinformationen zu diesem Beitrag sind im WWW unter http://dx.

A series of triarylmethyl palladium complexes with ortho coordination sites were synthesized. Thereby, the palladium atom exhibits various inter-and intramolecular binding modes towards the organic ligand. Further, the first crystallo-[a] Ruhr-53 graphically proven, exclusively σ-coordinated triarylmethyl palladium complexes, stabilized by ortho-thio-substituents, were discovered. The NMR spectra of the palladium complexes indicate temperature-dependent dynamic behavior.Scheme 1. General structures of triphenylmethyl complexes of alkaline and alkaline earth metals.