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Medientyp:
E-Artikel
Titel:
Oligonuclear Molecular Models of Intermetallic Phases: A Case Study on [Pd2Zn6Ga2(Cp*)5(CH3)3]
Beteiligte:
Bollermann, Timo;
Molon, Mariusz;
Gemel, Christian;
Freitag, Kerstin;
Seidel, Rüdiger W.;
von Hopffgarten, Moritz;
Jerabek, Paul;
Frenking, Gernot;
Fischer, Roland A.
Erschienen:
Wiley, 2012
Erschienen in:
Chemistry – A European Journal, 18 (2012) 16, Seite 4909-4915
Sprache:
Englisch
DOI:
10.1002/chem.201102758
ISSN:
0947-6539;
1521-3765
Entstehung:
Anmerkungen:
Beschreibung:
AbstractThe synthesis, characterization, and theoretical investigation by means of quantum‐chemical calculations of an oligonuclear metal‐rich compound are presented. The reaction of homoleptic dinuclear palladium compound [Pd2(μ‐GaCp*)3(GaCp*)2] with ZnMe2 resulted in the formation of unprecedented ternary Pd/Ga/Zn compound [Pd2Zn6Ga2(Cp*)5(CH3)3] (1), which was analyzed by 1H and 13C NMR spectroscopy, MS, elemental analysis, and single‐crystal X‐ray diffraction. Compound 1 consisted of two Cs‐symmetric molecular isomers, as revealed by NMR spectroscopy, at which distinct site‐preferences related to the Ga and Zn positions were observed by quantum‐chemical calculations. Structural characterization of compound 1 showed significantly different coordination environments for both palladium centers. Whilst one Pd atom sat in the central of a bi‐capped trigonal prism, thereby resulting in a formal 18‐valence electron fragment, {Pd(ZnMe)2(ZnCp*)4(GaMe)}, the other Pd atom occupied one capping unit, thereby resulting in a highly unsaturated 12‐valence electron fragment, {Pd(GaCp*)}. The bonding situation, as determined by atoms‐in‐molecules analysis (AIM), NBO partial charges, and molecular orbital (MO) analysis, pointed out that significant PdPd interactions had a large stake in the stabilization of this unusual molecule. The characterization and quantum‐chemical calculations of compound 1 revealed distinct similarities to related M/Zn/Ga Hume–Rothery intermetallic solid‐state compounds, such as Ga/Zn‐exchange reactions, the site‐preferences of the Zn/Ga positions, and direct MM bonding, which contributes to the overall stability of the metal‐rich compound.