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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 crystallographically 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Heterometalldotierte Goldcluster sind durch nasschemische Synthese schwer zugänglich, und mit Hauptgruppenmetallen oder frühen Übergangsmetallen dotierte Cluster sind rar. Die Verbindungen [M(AuPMe3)11(AuCl)]3+ (M=Pt, Pd, Ni) ( 1- 3), [Ni(AuPPh3)(8-2 n)(AuCl)3(AlCp*) n] ( n=1, 2) ( 4, 5) und [Mo(AuPMe3)8(GaCl2)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 [ClAuPR3] (R=Me, Ph) hergestellt und mit Einkristallröntgenbeugung 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. [ABSTRACT FROM AUTHOR]

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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. [ABSTRACT FROM AUTHOR]

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 (BArF = [B{C6H3(CF3)2}4) with GaCp* leads to [Cp*Fe(GaCp*)3][BArF] (1) via a redox neutral Cp* transfer and [Ga2Cp*][BArF] as a by-product while the formation of [Cp*Co(GaCp*)3][BArF]2 (2) from [Co(CH3CN)6][BArF]2 is accompanied by oxidation of Co(II) to Co(III) with GaCp* as the oxidant. The reactions of [Cu(CH3CN)4][BArF] and Ag[BPh4] with GaCp* lead to the formation of the homoleptic compounds [Cu(GaCp*)4][BArF] (4) and [Ag(GaCp*)4][BPh4] (5), while treatment of Ag[CF3SO3] with GaCp* leads to the dimeric complex [Ag2(GaCp*)3(μ-GaCp*)2][CF3SO3]2 (6). All compounds were characterized by NMR spectroscopy, single crystal X-ray diffraction and elemental analysis. [ABSTRACT FROM AUTHOR]