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Synthesis, Structure, and Reactivity of a Pyridine-Stabilized Germanone

Authors

  • Dr. Shenglai Yao,

    1. Institut für Chemie: Metalorganics and Inorganic Materials, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-29732
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  • Dr. Yun Xiong,

    1. Institut für Chemie: Metalorganics and Inorganic Materials, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-29732
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  • Wenyuan Wang,

    1. Institut für Chemie: Metalorganics and Inorganic Materials, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-29732
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  • Prof. Dr. Matthias Driess

    Corresponding author
    1. Institut für Chemie: Metalorganics and Inorganic Materials, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-29732
    • Institut für Chemie: Metalorganics and Inorganic Materials, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany), Fax: (+49) 30-314-29732
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Abstract

The first isolable pyridine-stabilized germanone has been prepared and its reactivity toward trimethylaluminum has been investigated. The germanone adduct results from a stepwise conversion that starts from 4-dimethylaminopyridine (DMAP) and the ylide-like N-heterocyclic germylene LGe: (L=CH{(C[DOUBLE BOND]CH2)(CMe)[N(aryl)]2}, aryl=2,6-iPr2C6H3) (1) at room temperature, and gives the corresponding germylene–pyridine adduct L(DMAP)Ge: (2) in 91 % yield. The latter reacts with N2O at room temperature to form the desired germanone complex L(DMAP)Ge[DOUBLE BOND]O (3) in 73 % yield. The Ge[BOND]O distance of 1.646(2) Å in 3 is the shortest hitherto reported for a Ge[DOUBLE BOND]O species. The reaction of 3 with trimethylaluminum leads solely to the addition product LGe(Me)O[Al(DMAP)Me2] (4). The latter results from insertion of the Ge[DOUBLE BOND]O subunit into an Al[BOND]Me bond of AlMe3 and concomitant migration of the DMAP ligand from germanium to the aluminum atom. Compounds 24 have been fully characterized by analytical and spectroscopic methods. Their molecular structures have been established by single-crystal X-ray crystallographic analysis.

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